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EP0379915A1 - Substituted phenoxybenzonitrile derivatives, processes for their preparation and their use as herbicides and plant growth regulators - Google Patents

Substituted phenoxybenzonitrile derivatives, processes for their preparation and their use as herbicides and plant growth regulators Download PDF

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Publication number
EP0379915A1
EP0379915A1 EP90100701A EP90100701A EP0379915A1 EP 0379915 A1 EP0379915 A1 EP 0379915A1 EP 90100701 A EP90100701 A EP 90100701A EP 90100701 A EP90100701 A EP 90100701A EP 0379915 A1 EP0379915 A1 EP 0379915A1
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EP
European Patent Office
Prior art keywords
chlorine
alkyl
fluorine
formula
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP90100701A
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German (de)
French (fr)
Inventor
Ulrich Dr. Busse
Hans-Joachim Dr. Santel
Robert R. Dr. Schmidt
Klaus Dr. Lürssen
Harry Dr. Strang
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Bayer AG
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Bayer AG
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Publication of EP0379915A1 publication Critical patent/EP0379915A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/08—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C07C255/59—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C07C255/60—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton at least one of the singly-bound nitrogen atoms being acylated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/32—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
    • C07C275/34—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms having nitrogen atoms of urea groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C275/36—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms having nitrogen atoms of urea groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring with at least one of the oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. N-aryloxyphenylureas

Definitions

  • the invention relates to new substituted phenoxybenzonitrile derivatives, processes for their preparation and their use as herbicides and plant growth regulators.
  • the substituted phenoxybenzonitrile derivatives of the formula (I) according to the invention are more potent against weeds than methyl 3- (2,4-dichlorophenoxy) -6-nitro-benzoate, which is a structurally similar previously known active ingredient with the same direction of action .
  • the invention preferably relates to compounds of the formula (I) in which R1 represents hydrogen, fluorine, chlorine, bromine, cyano or trifluoromethyl, R2 represents hydrogen, fluorine or chlorine, R3 represents fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl, R4 represents hydrogen, fluorine or chlorine, R5 represents hydrogen, fluorine or chlorine and R6 for the groupings or stands in what R7 and R8 are the same or different and each independently represent hydrogen, C1-C6-alkoxy-carbonyl-ethyl, the grouping -CO-R9 or the grouping -SO2-R19, where R9 for C1-C6-alkyl optionally substituted by fluorine, chlorine, bromine, C1-C4-alkoxy and / or C1-C4-alkoxy-carbonyl, for C2-C4-alkenyl optionally substituted by fluorine, chlorine and / or
  • the invention relates in particular to compounds of the formula (I) in which R1 represents hydrogen, fluorine or chlorine, in particular chlorine, R2 represents hydrogen, fluorine or chlorine, in particular hydrogen, R3 represents trifluoromethyl, R4 represents hydrogen, fluorine or chlorine, in particular hydrogen, R5 represents hydrogen, fluorine or chlorine, in particular fluorine or chlorine and R6 for the groupings or stands in what R7 represents hydrogen or acetyl and R8 represents hydrogen, methoxycarbonylethyl, ethoxycarbonylethyl, the grouping -CO-R9 or the grouping -SO2-R10, wherein R9 for C1-C4-alkyl optionally substituted by chlorine, bromine, methoxy or ethoxy, for cyclopropyl, for benzyl, for phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy and / or ethoxy, for C1-C4- Alkoxy
  • Formula (II) provides a general definition of the halogenobenzene derivatives to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I).
  • R1, R2, R3, R4 and R5 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R1, R2, R3 , R4 and R5 have been specified and X preferably represents fluorine or chlorine.
  • the compounds to be used as starting materials in the processes (b), (c) and (d) according to the invention are generally defined by the formula (I) with the proviso that R6 is amino.
  • the radicals R1, R2, R3, R4 and R5 preferably or in particular have those meanings which have already been given as preferred or as particularly preferred in the context of the description of the compounds of the formula (I) according to the invention.
  • R9 and R10 preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R9 and R10 and X1 as well as X2 are preferably fluorine, chlorine or bromine, in particular chlorine.
  • Examples of the starting materials of the formulas (IV) and (V) are: Acetylchloride, propionylchloride, butyroylchloride, isobutyroylchloride, valeroylchloride, isovaleroylchloride, chloroacetylchloride, dichloroacetylchloride, trichloroacetylchloride, 2-chloropropionylchloride, 2-bromopropionylchloride, methoxyacetylchloride, ethoxyacetylchloride, 2-methoxypropylchloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-meth
  • the starting materials of the formula (IV) and (V) are known compounds.
  • Formula (VI) provides a general definition of the acrylic acid esters to be used as starting materials in processes (c) and (d) according to the invention.
  • R12 is preferably C1-C6 alkyl, especially C1-C4 alkyl.
  • the compounds of formula (VI) are known organic synthetic chemicals.
  • the compounds to be used as starting materials in process (e) according to the invention are represented by the formula (I) with the proviso that R6 for the grouping stands, generally defined.
  • the radicals R1, R2, R3, R4, R5 and R12 preferably or in particular have those meanings which have already been given in the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred and R11 is above preferably for chlorine or bromine.
  • Process (a) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents.
  • diluents Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and Dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobut
  • aprotic polar solvents such as. B. acetone, acetonitrile, methyl ethyl ketone, propionitrile, methyl isobutyl ketone, methyl isopropyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, particularly preferred.
  • Acid acceptors which can be used in process (a) according to the invention are all acid binders which can customarily be used for such reactions.
  • Alkali metal hydroxides such as, for. B. sodium and potassium hydroxide, alkaline earth metal hydroxides such. B.
  • alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium and potassium tert-butoxide, also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo- [4 , 3,0] non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2 ] octane (DABCO).
  • DBN 1,5-diazabicyclo- [4 , 3,0] non-5-ene
  • DBU 1,8-diazabicyclo- [5,4,0] -undec-7-ene
  • DABCO 1,4-diazabicyclo- [2,2,2 ] octane
  • reaction temperatures in process (a) according to the invention can be varied within a substantial range. In general, temperatures between 0 ° C and 200 ° C, preferably at temperatures between 20 ° C and 120 ° C.
  • Process (a) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • process (a) the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess.
  • the reactions are generally carried out in a suitable diluent in the presence of an acid Acceptor performed, and the reaction mixture is stirred for several hours at the required temperature.
  • Working up in process (a) according to the invention is carried out in each case by customary methods.
  • Process (b) according to the invention for the preparation of the new compounds of the formula (I) is optionally carried out using diluents.
  • Suitable diluents here are all inert organic solvents as specified above for process (a) according to the invention.
  • Process (b) is optionally carried out in the presence of an acid acceptor.
  • Suitable acid acceptors here are virtually all acid binders which can usually be used for such reactions, as indicated above for process (a) according to the invention.
  • reaction temperatures can be varied within a substantial range in process (b) according to the invention. In general, temperatures between -20 ° C and +150 ° C, preferably at temperatures between 0 ° C and 100 ° C.
  • Process (b) according to the invention is generally carried out under normal pressure. However, it is also possible Lich to work under increased or reduced pressure.
  • process (b) the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess.
  • the reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case.
  • Working up in process (b) according to the invention is carried out by customary methods.
  • Process (c) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents.
  • diluents Practically all inert organic solvents as specified above for process (a) according to the invention are suitable as diluents. Of these, the aprotic polar solvents indicated above are particularly preferred.
  • Process (c) is optionally carried out in the presence of a basic catalyst.
  • Suitable basic catalysts are alkali metal hydroxides or alcoholates, such as sodium or potassium hydroxide, methylate, ethylate or tert-butoxide, alkali metal salts of carboxylic acids, such as. B. sodium or potassium acetate, and basic nitrogen compounds such as diethylamine or piperidine.
  • reaction temperatures can be varied within a substantial range in process (c) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C.
  • Process (c) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • process (c) the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess.
  • the reactions are generally carried out in a suitable diluent in the presence of a basic catalyst, and the reaction mixture is stirred for several hours at the temperature required in each case.
  • Working up in process (c) according to the invention is carried out by customary methods.
  • Process (d) according to the invention for the preparation of compounds of the formula (I) is carried out using a hydrogen halide (HX 3).
  • HX 3 hydrogen halide
  • Examples of these are hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide. Hydrogen chloride and hydrogen bromide are preferably used.
  • Process (d) is preferably carried out using an organic solvent.
  • organic solvent particularly suitable are ethers, such as glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as. B. acetone and methyl ethyl ketone, and amides such as. B. Dimethylformamide.
  • Process (d) is further preferably carried out in the presence of catalysts.
  • catalysts As such come in particular copper and copper compounds such.
  • reaction temperatures can be varied within a substantial range in process (d) according to the invention. In general, temperatures between -20 ° C and +80 ° C, preferably at temperatures between 0 ° C and 60 ° C.
  • Process (d) is generally carried out under normal pressure.
  • process (d) generally between 0.8 and 2.5 mol, preferably between 1.1 and 2.0 mol, sodium nitrite or potassium nitrite, between 2 and 50 mol are used per mol of phenoxyphenylamino compound of the formula (I) , preferably between 5 and 25 mol, hydrogen halide, and between 1 and 3 mol, preferably between 1.5 and 2.5 mol, acrylic acid derivative of the formula (VI).
  • Process (d) can be carried out under the usual conditions of "sea wine arylation".
  • the starting compound of the formula (I) is first stirred in a diluent which comprises at least water and a hydrogen halide and diazotized with cooling with an aqueous solution of sodium nitrite or potassium nitrite.
  • the acrylic acid derivative of the formula (VI) and optionally the catalyst are added to the reaction mixture.
  • Process (e) according to the invention for the preparation of compounds of the formula (I) is carried out using a dehalogenating agent.
  • a dehalogenating agent can be the usual substances suitable for dehalogenation, such as. B. tributyltin hydride can be used.
  • Process (e) is optionally carried out in the presence of a catalyst.
  • catalysts here come as free radical initiators, such as. B. azo-bis-isobutyronitrile, into consideration.
  • Process (e) is preferably carried out in the presence of a diluent.
  • a diluent Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene, and ethers, such as diethyl ether, dipro pyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane.
  • reaction temperatures can be varied within a substantial range in process (e) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 10 ° C and 100 ° C.
  • Process (e) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • process (e) the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess.
  • the reactions are generally carried out in a suitable diluent in the presence of a catalyst and the reaction mixture is stirred for several hours at the temperature required in each case.
  • Working up in process (e) according to the invention is carried out in each case by customary methods.
  • the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants hen who grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the active compounds according to the invention can be used, for example, in the following plants: Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
  • the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops e.g. Forests, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annual crops.
  • the compounds according to the invention are particularly suitable for the selective control of dicotyledon weeds in monocotyledon crops, especially in the wake process.
  • the active compounds according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators.
  • plant growth regulators According to previous experience, the principle of action of plant growth regulators is that an active ingredient can also have several different effects on plants.
  • the effects of the substances essentially depend on the point in time of use, based on the stage of development of the plant, on the amounts of active ingredient applied to the plants or their environment and on the type of application. In any case growth regulators are intended to influence the crop plants in a desired manner.
  • the amount of leaves in the plants can be controlled in such a way that defoliation of the plants is achieved at a desired point in time.
  • defoliation plays a large role in the mechanical harvesting of cotton, but is also important in other crops, such as e.g. of interest in viticulture to facilitate harvesting.
  • Defoliation of the plants can also be carried out in order to reduce the transpiration of the plants before transplanting.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
  • formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • Com as liquid solvent Men essentially in question: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or Glycol and its ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlor
  • solid carriers e.g. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granulates are possible: e.g.
  • suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • dispersants for example lignin sulfite waste liquor and methyl cellulose.
  • Adhesives such as carboxy can be used in the formulations methyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with known herbicides for weed control, finished formulations or tank mixes being possible.
  • Known herbicides such as 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1, 3,5-triazine-2,4 (1H, 3H) -dione (AMETHYDIONE) or N- (2-benzothiazolyl) -N, N'-dimethyl-urea (METABENZTHIAZURON) for weed control in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one (METAMITRON) for weed control in sugar beets and 4-amino-6- (1,1-dimethylethyl) -3- methylthio-1,2,4-triazin-5 (4H) -one (METRIBUZIN) for weed control in soybeans, in question; also 2,4-Di chlorophenoxyacetic acid (2,4-D); 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB); 2,4-dich
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
  • the active compounds according to the invention can be applied both before and after emergence of the plants.
  • the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
  • the concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 2000 l of water / ha.
  • the compounds according to preparation examples (2) and (4) show considerably stronger activity than the known compound (A) against weeds, such as. B. Ipomoea, Sida, Sinapis and Viola.
  • Emulsifier 1 part by weight of polyoxyethylene sorbitan monolaurate
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.
  • Cotton plants are grown in the greenhouse until the 5th following leaf is fully developed. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 1 week, the leaf fall and the drying out of the leaves are rated in comparison to the control plants.
  • the active ingredients according to the preparation examples (3) and (4) show very strong drying out of the leaves and very strong falling of the leaves.

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Abstract

The invention relates to novel substituted phenoxybenzonitrile derivatives of the formula (I) <IMAGE> in which R<1> represents hydrogen, halogen, cyano or trifluoromethyl, R<2> represents hydrogen or halogen, R<3> represents halogen, trifluoromethyl, trifluoromethoxy or trifluoromethylsulphonyl, R<4> represents hydrogen or halogen, R<5> represents hydrogen or halogen and R<6> represents the groups <IMAGE> or <IMAGE> as well as several processes for their preparation, and their use as herbicides and plant growth regulators.

Description

Die Erfindung betrifft neue substituierte Phenoxybenzo­nitril-Derivate, Verfahren zu ihrer Herstellung sowie ihre Verwendung als Herbizide und Pflanzenwuchsregula­toren.The invention relates to new substituted phenoxybenzonitrile derivatives, processes for their preparation and their use as herbicides and plant growth regulators.

Es ist bereits bekannt, daß bestimmte Phenoxybenzoesäu­re-Derivate, wie z. B. 3-(2,4-Dichlor-phenoxy)-6-nitro­benzoesäure-methylester (Bifenox) herbizid wirksam sind (vgl. US-P 3 652 645 und US-P 3 776 715). Die Wirkung dieser bekannten Verbindungen ist jedoch nicht immer zu­friedenstellend.It is already known that certain phenoxybenzoic acid derivatives, such as. B. 3- (2,4-dichlorophenoxy) -6-nitrobenzoic acid methyl ester (bifenox) are herbicidal (cf. US Pat. No. 3,652,645 and US Pat. No. 3,776,715). However, the action of these known compounds is not always satisfactory.

Es wurden nun neue substituierte Phenoxybenzonitril-­Derivate der allgemeinen Formel (I)

Figure imgb0001
in welcher
R¹ für Wasserstoff, Halogen, Cyano oder Trifluormethyl steht,
R² für Wasserstoff oder Halogen steht,
R³ für Halogen, Trifluormethyl, Trifluormethoxy oder Trifluormethylsulfonyl steht,
R⁴ für Wasserstoff oder Halogen steht,
R⁵ für Wasserstoff oder Halogen steht und
R⁶ für die Gruppierungen
Figure imgb0002
 oder
Figure imgb0003
 steht, worin
R⁷ und R⁸ gleich oder verschieden sind und unab­hängig voneinander jeweils für Wasserstoff, Alkoxycarbonylethyl, die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ stehen, wobei
R⁹ für jeweils gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkylalkyl, Benzyl, Phenyl, Naphthyl, Pyridyl, Furyl, Thienyl, Alkoxy, Phenoxy, Alkylthio, Phenylthio, Alkylamino, Dialkylamino, Cycloalkylamino oder Phenylamino steht und
R¹⁰ für jeweils gegebenenfalls substituiertes Alkyl, Phenyl, Naphthyl, Pyridyl oder Thienyl steht,
R¹¹ für Wasserstoff oder Halogen steht und
R¹² für Alkyl steht,
gefunden.New substituted phenoxybenzonitrile derivatives of the general formula (I)
Figure imgb0001
 in which
R¹ represents hydrogen, halogen, cyano or trifluoromethyl,
R² represents hydrogen or halogen,
R³ represents halogen, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl,
R⁴ represents hydrogen or halogen,
R⁵ represents hydrogen or halogen and
R⁶ for the groupings
Figure imgb0002
 or
Figure imgb0003
 stands in what
R⁷ and R⁸ are the same or different and each independently represent hydrogen, alkoxycarbonylethyl, the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, where
R⁹ represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, benzyl, phenyl, naphthyl, pyridyl, furyl, thienyl, alkoxy, phenoxy, alkylthio, phenylthio, alkylamino, dialkylamino, cycloalkylamino or phenylamino and
R¹⁰ represents optionally substituted alkyl, phenyl, naphthyl, pyridyl or thienyl,
R¹¹ represents hydrogen or halogen and
R¹² represents alkyl,
found.

Weiter wurde gefunden, daß man die neuen substituierten Phenoxybenzonitril-Derivate der allgemeinen Formel (I) erhalt, wenn man

  • (a) für den Fall, daß in Formel (I) R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Be­deutungen haben,
    Halogen-benzol-Derivate der allgemeinen Formel (II)
    Figure imgb0004
     in welcher
    R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben und
    X für Halogen steht,
    mit 2-Amino-4-hydroxy-benzonitril der Formel (III)
    Figure imgb0005
     gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man
  • (b) für den Fall, daß in Formel (I) R⁶ für die Gruppierung
    Figure imgb0006
     steht, worin R⁷ und/oder R⁸ für die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ stehen, und R¹, R², R³, R⁴, R⁵, R⁹ und R¹⁰ die oben angegebene Bedeutung haben,
    Verbindungen der allgemeinen Formel (I), in welcher R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
    mit Verbindungen der allgemeinen Formel (IV)
    X¹-CO-R⁹      (IV)
    in welcher
    R⁹ die oben angegebene Bedeutung hat und
    X¹ für Halogen steht,
    oder mit Verbindungen der allgemeinen Formel (V)
    X²-SO₂-R¹⁰      (V)
    in welcher
    R¹⁰ die oben angegebene Bedeutung hat und
    X² für Halogen steht,
    gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man
  • (c) für den Fall, daß in Formel (I) R⁶ für die Guppierung
    Figure imgb0007
     steht, worin R⁷ und/oder R⁸ für Alkoxycarbonylethyl stehen, und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
    Verbindungen der allgemeinen Formel (I), in welcher R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
    mit Acrylsäureestern der Formel (VI)
    CH₂=CH-COOR¹²      (VI)
    in welcher
    R¹² für Alkyl steht,
    gegebenenfalls in Gegenwart eines basischen Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder wenn man
  • (d) für den Fall, daß in Formel (I) R⁶ für die Gruppie­rung
    Figure imgb0008
     steht, worin R¹¹ für Halogen steht und R¹² für Alkyl steht sowie R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
    Verbindungen der allgemeinen Formel (I), in welcher R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
    mit Natriumnitrit oder Kaliumnitrit und mit einem Hydrogenhalogenid (HX³) in Gegenwart von Wasser und gegebenenfalls in Gegenwart eines organischen Lö­sungsmittels umsetzt und die hierbei gebildeten Diazoniumsalze der allgemeinen Formel (VII)
    Figure imgb0009
     in welcher
    R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeu­tungen haben und
    X³ für Halogen steht,
    mit Acrylsäureestern der Formel (VI)
    CH₂=CH-COOR¹²      (VI)
    in welcher
    R¹² für Alkyl steht,
    in Gegenwart von Hydrogenhalogeniden (HX³), gegebenen­falls in Gegenwart von Katalysatoren und gegebenenfalls in Gegenwart von Wasser und dem gegebenenfalls bei der Erzeugung der Verbindungen der Formel (VII) verwendeten organischen Lösungsmittel umsetzt, oder wenn man
  • (e) für den Fall, daß in Formel (I) R⁶ für die Gruppie­rung
    Figure imgb0010
     steht, worin R¹¹ für Wasser­stoff steht und R¹² für Alkyl steht sowie R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
    Verbindungen der allgemeinen Formel (I), in welcher
    R⁶ für die Gruppierung
    Figure imgb0011
     steht, worin R¹¹ für Halogen steht und R¹² für Alkyl steht sowie R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeu­tungen haben,
    mit einem Dehalogenierungsmittel, gegebenenfalls in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels, umsetzt.
It was also found that the new substituted phenoxybenzonitrile derivatives of the general formula (I) are obtained if
  • (a) in the case that in formula (I) R⁶ is amino and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
    Halogen benzene derivatives of the general formula (II)
    Figure imgb0004
     in which
    R¹, R², R³, R⁴ and R⁵ have the meanings given above and
    X represents halogen,
    with 2-amino-4-hydroxy-benzonitrile of the formula (III)
    Figure imgb0005
     if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
  • (b) in the event that in formula (I) R⁶ for the grouping
    Figure imgb0006
     in which R⁷ and / or R⁸ represent the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, and R¹, R², R³, R⁴, R⁵, R⁹ and R¹⁰ have the meaning given above,
    Compounds of the general formula (I) in which R⁶ represents amino and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
    with compounds of the general formula (IV)
    X¹-CO-R⁹ (IV)
    in which
    R⁹ has the meaning given above and
    X¹ represents halogen,
    or with compounds of the general formula (V)
    X²-SO₂-R¹⁰ (V)
    in which
    R¹⁰ has the meaning given above and
    X² represents halogen,
    if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or if
  • (c) in the event that in formula (I) R⁶ for the grouping
    Figure imgb0007
     in which R⁷ and / or R⁸ are alkoxycarbonylethyl, and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
    Compounds of the general formula (I) in which R⁶ is amino and R¹, R², R³, R⁴ and R⁵ are have the meanings given above,
    with acrylic acid esters of the formula (VI)
    CH₂ = CH-COOR¹² (VI)
    in which
    R¹² represents alkyl,
    if appropriate in the presence of a basic catalyst and if appropriate in the presence of a diluent, or if
  • (d) in the event that in formula (I) R⁶ for the grouping
    Figure imgb0008
     in which R¹¹ is halogen and R¹² is alkyl and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
    Compounds of the general formula (I) in which R⁶ represents amino and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
    with sodium nitrite or potassium nitrite and with a hydrogen halide (HX³) in the presence of water and optionally in the presence of an organic solvent and the diazonium salts of the general formula (VII) formed in this way
    Figure imgb0009
     in which
    R¹, R², R³, R⁴ and R⁵ have the meanings given above and
    X³ represents halogen,
    with acrylic acid esters of the formula (VI)
    CH₂ = CH-COOR¹² (VI)
    in which
    R¹² represents alkyl,
    in the presence of hydrogen halides (HX³), if appropriate in the presence of catalysts and if appropriate in the presence of water and the organic solvent optionally used in the preparation of the compounds of the formula (VII), or if
  • (e) in the event that in formula (I) R⁶ for the grouping
    Figure imgb0010
     in which R¹¹ is hydrogen and R¹² is alkyl and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
    Compounds of the general formula (I) in which
    R⁶ for grouping
    Figure imgb0011
     in which R¹¹ is halogen and R¹² is alkyl and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
    with a dehalogenating agent, optionally in the presence of a catalyst and optionally in the presence of a diluent.

Schließlich wurde gefunden, daß die neuen substituierten Phenoxybenzonitril-Derivate der Formel (I) hervorragende herbizide bzw. pflanzen­wuchsregulierende Eigenschaften aufweisen.Finally, it was found that the new substituted phenoxybenzonitrile derivatives of the formula (I) have excellent herbicidal or plant growth-regulating properties.

Überraschenderweise sind die erfindungsgemäßen substituierten Phenoxybenzonitril-Derivate der For­mel (I) gegen Unkräuter wesentlich stärker wirksam als 3-(2,4-Dichlor-phenoxy)-6-nitro-benzoe-säure-­methylester, welches ein strukturell ähnlicher vorbekannter Wirkstoff gleicher Wirkungsrichtung ist.Surprisingly, the substituted phenoxybenzonitrile derivatives of the formula (I) according to the invention are more potent against weeds than methyl 3- (2,4-dichlorophenoxy) -6-nitro-benzoate, which is a structurally similar previously known active ingredient with the same direction of action .

Die Erfindung betrifft vorzugsweise Verbindungen der Formel (I), in welcher
R¹ für Wasserstoff, Fluor, Chlor, Brom, Cyano oder Trifluormethyl steht,
R² für Wasserstoff, Fluor oder Chlor steht,
R³ für Fluor, Chlor, Brom, Trifluormethyl, Trifluormethoxy oder Trifluormethylsulfonyl steht,
R⁴ für Wasserstoff, Fluor oder Chlor steht,
R⁵ für Wasserstoff, Fluor oder Chlor steht und
R⁶ für die Gruppierungen

Figure imgb0012
oder
Figure imgb0013
 steht, worin
R⁷ und R⁸ gleich oder verschieden sind und unabhängig voneinander jeweils für Was­serstoff, C₁-C₆-Alkoxy-carbonyl-ethyl, die Gruppierung -CO-R⁹ oder die Gruppie­rung -SO₂-R¹⁹ stehen, wobei
R⁹ für gegebenenfalls durch Fluor, Chlor, Brom, C₁-C₄-Alkoxy und/oder C₁-C₄-Alkoxy-carbonyl substituiertes C₁-C₆-Alkyl, für gegebenenfalls durch Fluor, Chlor und/oder Brom substituier­tes C₂-C₄-Alkenyl, für C₂-C₄-Alkinyl, für ge­gebenenfalls durch Fluor, Chlor, Brom, C₁-C₄­Alkyl und/oder C₁-C₄-Alkoxy-carbonyl substi­ tuiertes C₃-C₆-Cycloalkyl, für gegebenenfalls durch Fluor, Chlor, Brom und/oder C₁-C₄-Alkyl substituiertes C₃-C₆-Cycloalkyl-C₁-C₂-alkyl, für gegebenenfalls durch Fluor, Chlor, Brom, C₁-C₄-Alkyl und/oder C₁-C₄-Alkoxy substituier­tes Benzyl, für gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C₁-C₄-Alkyl und/­oder C₁-C₄-Alkoxy substituiertes Phenyl, für Naphthyl, für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro und/oder C₁-­C₄-Alkyl substituiertes Pyridyl, Furyl oder Thienyl, für C₁-C₆-Alkoxy, Phenoxy, C₁-C₆-­Alkylthio, Phenylthio, C₁-C₆-Alkyl-amino, Di-­(C₁-C₄)-alkylamino, C₃C₆-Cycloalkylamino oder für gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C₁-C₄-Alkyl, Trifluormethyl, C₁-­C₄-Alkoxy und/oder C₁-C₄-Alkoxy-carbonyl sub­stituiertes Phenylamino steht und
R¹⁰ für gegebenenfalls durch Fluor und/oder Chlor substituiertes C₁-C₆-Alkyl, für gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C₁-C₄-­Alkyl, Trifluormethyl, C₁-C₄-Alkoxy, Difluor­methoxy, Trifluormethoxy, C₁-C₄-Alkylthio, C₁-­C₄- Alkylsulfinyl, C₁-C₄-Alkylsulfonyl, Di-­(C₁-C₂)alkylaminosulfonyl und/oder C₁-C₄-­Alkoxy-carbonyl substituiertes Phenyl, für gegebenenfalls durch Chlor und/oder C₁-C₄-­Alkyl substituiertes Naphtyl oder für jeweils gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro und/oder C₁-C₄-Alkyl substi­tuiertes Pyridyl oder Thienyl steht,
R¹¹ für Wasserstoff, Chlor oder Brom steht und
R¹² für C₁-C₆-Alkyl steht.The invention preferably relates to compounds of the formula (I) in which
R¹ represents hydrogen, fluorine, chlorine, bromine, cyano or trifluoromethyl,
R² represents hydrogen, fluorine or chlorine,
R³ represents fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl,
R⁴ represents hydrogen, fluorine or chlorine,
R⁵ represents hydrogen, fluorine or chlorine and
R⁶ for the groupings
Figure imgb0012
 or
Figure imgb0013
 stands in what
R⁷ and R⁸ are the same or different and each independently represent hydrogen, C₁-C₆-alkoxy-carbonyl-ethyl, the grouping -CO-R⁹ or the grouping -SO₂-R¹⁹, where
R⁹ for C₁-C₆-alkyl optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkoxy and / or C₁-C₄-alkoxy-carbonyl, for C₂-C₄-alkenyl optionally substituted by fluorine, chlorine and / or bromine, for C₂-C₄-alkynyl, optionally substituted by fluorine, chlorine, bromine, C₁-C₄alkyl and / or C₁-C₄-alkoxy-carbonyl Tuiert C₃-C₆-cycloalkyl, for optionally substituted by fluorine, chlorine, bromine and / or C₁-C₄-alkyl substituted C₃-C₆-cycloalkyl-C₁-C₂-alkyl, for optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl and / or C₁-C₄-alkoxy substituted benzyl, for phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl and / or C₁-C₄-alkoxy, for naphthyl, each optionally substituted by fluorine, chlorine , Bromine, cyano, nitro and / or C₁-C₄-alkyl substituted pyridyl, furyl or thienyl, for C₁-C₆-alkoxy, phenoxy, C₁-C₆-alkylthio, phenylthio, C₁-C₆-alkyl-amino, di- (C₁ -C₄) alkylamino, C₃C₆ cycloalkylamino or phenylamino optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy and / or C₁-C₄-alkoxy-carbonyl and
R¹⁰ for optionally substituted by fluorine and / or chlorine C₁-C₆-alkyl, for optionally by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy, difluoromethoxy, trifluoromethoxy, C₁-C₄ -Alkylthio, C₁-C₄- alkylsulfinyl, C₁-C₄-alkylsulfonyl, di- (C₁-C₂) alkylaminosulfonyl and / or C₁-C₄-alkoxycarbonyl substituted phenyl, for optionally substituted by chlorine and / or C₁-C₄-alkyl naphthyl or represents in each case optionally substituted by fluorine, chlorine, bromine, cyano, nitro and / or C₁-C₄-alkyl pyridyl or thienyl,
R¹¹ represents hydrogen, chlorine or bromine and
R¹² is C₁-C₆ alkyl.

Die Erfindung betrifft insbesondere Verbindungen der Formel (I), in welcher
R¹ für Wasserstoff, Fluor oder Chlor, insbesondere für Chlor steht,
R² für Wasserstoff, Fluor oder Chlor, insbesondere für Wasserstoff steht,
R³ für Trifluormethyl steht,
R⁴ für Wasserstoff, Fluor oder Chlor, insbesondere für Wasserstoff steht,
R⁵ für Wasserstoff, Fluor oder Chlor, insbesondere für Fluor oder Chlor steht und
R⁶ für die Gruppierungen

Figure imgb0014
oder
Figure imgb0015
 steht, worin
R⁷ für Wasserstoff oder Acetyl steht und
R⁸ für Wasserstoff, Methoxycarbonylethyl, Ethoxycarbonylethyl, die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ steht, wobei
R⁹ für gegebenenfalls durch Chlor, Brom, Methoxy oder Ethoxy substituiertes C₁-C₄-­Alkyl, für Cyclopropyl, für Benzyl, für gegebenenfalls durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy und/oder Ethoxy substituiertes Phenyl, für C₁-C₄-Alkoxy, Phenoxy, C₁-C₄-Alkylamino, Dimethyl­amino, Diethylamino, Cyclopentylamino, Cyclohexylamino oder für gegegebenenfalls durch Fluor, Chlor, Methyl, Ethyl, Tri­fluormethyl, Methoxy und/oder Ethoxy sub­stituiertes Phenylamino steht und
R¹⁰ für gegebenenfalls durch Fluor und/oder Chlor substituiertes C₁-C₄-Alkyl, für gegebenenfalls durch Fluor, Chlor, Brom, Methyl, Trifluormethoxy, Dimethylamino­sulfonyl und/oder Methoxycarbonyl sub­stituiertes Phenyl steht,
R¹¹ für Wasserstoff, Chlor oder Brom steht und
R¹² für C₁-C₄-Alkyl steht.The invention relates in particular to compounds of the formula (I) in which
R¹ represents hydrogen, fluorine or chlorine, in particular chlorine,
R² represents hydrogen, fluorine or chlorine, in particular hydrogen,
R³ represents trifluoromethyl,
R⁴ represents hydrogen, fluorine or chlorine, in particular hydrogen,
R⁵ represents hydrogen, fluorine or chlorine, in particular fluorine or chlorine and
R⁶ for the groupings
Figure imgb0014
 or
Figure imgb0015
 stands in what
R⁷ represents hydrogen or acetyl and
R⁸ represents hydrogen, methoxycarbonylethyl, ethoxycarbonylethyl, the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, wherein
R⁹ for C₁-C₄-alkyl optionally substituted by chlorine, bromine, methoxy or ethoxy, for cyclopropyl, for benzyl, for phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy and / or ethoxy, for C₁-C₄- Alkoxy, phenoxy, C₁-C₄-alkylamino, dimethylamino, diethylamino, cyclopentylamino, cyclohexylamino or phenylamino optionally substituted by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy and / or ethoxy and
R¹⁰ represents C₁-C₄-alkyl optionally substituted by fluorine and / or chlorine, represents phenyl optionally substituted by fluorine, chlorine, bromine, methyl, trifluoromethoxy, dimethylaminosulfonyl and / or methoxycarbonyl,
R¹¹ represents hydrogen, chlorine or bromine and
R¹² is C₁-C₄ alkyl.

Beispiele für die erfindungsgemäßen Verbindungen der Formel (I) sind in der nachstehenden Tabelle 1 aufge­führt (vgl. auch die Herstellungsbeispiele).

Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
 Examples of the compounds of the formula (I) according to the invention are listed in Table 1 below (cf. also the preparation examples).
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020

Verwendet man für das erfindungsgemäße Verfahren (a) beispielsweise 3,4-Dichlor-benzotrifluorid und 2-Amino-­4-hydroxy-benzonitril als Ausgangsstoffe, so kann der Reaktionsablauf durch das folgende Formelschema wieder­gegeben werden:

Figure imgb0021
If, for example, 3,4-dichlorobenzotrifluoride and 2-amino-4-hydroxy-benzonitrile are used as starting materials for process (a) according to the invention, the course of the reaction can be represented by the following formula:
Figure imgb0021

Verwendet man für das erfindungsgemäße Verfahren (b) beispielsweise 2-Amino-4-(2,6-difluor-4-trifluormethyl-­phenoxy)-benzonitril und Dichloracetylchlorid als Aus­gangsstoffe, so kann der Reaktionsablauf durch das fol­gende Formelschema wiedergegeben werden:

Figure imgb0022
If, for example, 2-amino-4- (2,6-difluoro-4-trifluoromethyl-phenoxy) -benzonitrile and dichloroacetyl chloride are used as starting materials for process (b) according to the invention, the course of the reaction can be represented by the following formula:
Figure imgb0022

Verwendet man für das erfindungsgemäße Verfahren (c) beispielsweise 2-Amino-4-(2,3,6-Trichlor-4-trifluor­methyl-phenoxy)-benzonitril und Acrylsäurebutylester als Ausgangsstoffe, so kann der Reaktionsablauf durch das folgende Formelschema wiedergegeben werden:

Figure imgb0023
If, for example, 2-amino-4- (2,3,6-trichloro-4-trifluoromethylphenoxy) benzonitrile and butyl acrylate are used as starting materials for process (c) according to the invention, the course of the reaction can be carried out by the following formula scheme is shown:
Figure imgb0023

Verwendet man für das erfindungsgemäße Verfahren (d) beispielsweise 2-Amino-4-(2-Chlor-6-fluor-4-trifluor­methyl-phenoxy)-benzonitril, Natriumnitrit und Salzsäure sowie anschließend Acrylsäure-isopropylester als Aus­gangsstoffe, so kann der Reaktionsablauf durch das fol­gende Formelschema wiedergegeben werden:

Figure imgb0024
If, for example, 2-amino-4- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) benzonitrile, sodium nitrite and hydrochloric acid and then isopropyl acrylic acid are used as starting materials for process (d) according to the invention, the reaction can be carried out by the following formula scheme can be reproduced:
Figure imgb0024

Verwendet man für das erfindungsgemäße Verfahren (e) beispielsweise 2-Chlor-3-[2-cyano-5-(2,6-dichlor-4-tri­ fluormethyl-phenoxy)-phenyl]-propionsäure-ethylester und Tributylzinnhydrid als Ausgangsstoffe, so kann der Reak­tionsablauf durch das folgende Formelschema wiederge­geben werden:

Figure imgb0025
If, for example, 2-chloro-3- [2-cyano-5- (2,6-dichloro-4-tri fluoromethyl-phenoxy) -phenyl] -propionic acid ethyl ester and tributyltin hydride as starting materials, the course of the reaction can be represented by the following formula:
Figure imgb0025

Die beim erfindungsgemäßen Verfahren (a) zur Herstellung von Verbindungen der Formel (I) als Ausgangsstoffe zu verwendenden Halogen-benzol-Derivate sind durch die For­mel (II) allgemein definiert.Formula (II) provides a general definition of the halogenobenzene derivatives to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I).

In Formel (II) haben R¹, R², R³, R⁴ und R⁵ vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfin­dungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevorzugt für R¹, R², R³, R⁴ und R⁵ angegeben wurden und X steht vorzugsweise für Fluor oder Chlor.In formula (II), R¹, R², R³, R⁴ and R⁵ preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R¹, R², R³ , R⁴ and R⁵ have been specified and X preferably represents fluorine or chlorine.

Als Beispiele für die Ausgangsstoffe der Formel (II) seien genannt:
3,4-Dichlor-benzotrifluorid, 3,4,5-Trichlor-benzotri­fluorid, 3,4-Dichlor-5-fluor-benzotrifluorid, 2,3,4,5-­Tetrachlor-benzotrifluorid, 3,5-Dichlor-2,4-difluor-ben­zotrifluorid und 3-Chlor-4,5-difluor-benzotrifluorid.The following may be mentioned as examples of the starting materials of the formula (II):
3,4-dichloro-benzotrifluoride, 3,4,5-trichloro-benzotrifluoride, 3,4-dichloro-5-fluoro-benzotrifluoride, 2,3,4,5-tetrachloro-benzotrifluoride, 3,5-dichloro-2, 4-difluoro-benzotrifluoride and 3-chloro-4,5-difluoro-benzotrifluoride.

Die Verbindungen der Formel (II) sind bekannt und/oder können nach an sich bekannten Verfahren hergestellt wer­den (vgl. J. Chem. Soc. 1969, 211-217; ibid. 1971, FR-A 2 538 380 (Chem. Abstracts 102 (1985), 61914x); EP-A 180 057; US-P 4 388 472).The compounds of the formula (II) are known and / or can be prepared by processes known per se (cf. J. Chem. Soc. 1969, 211-217; ibid. 1971, FR-A 2 538 380 (Chem. Abstracts 102 (1985), 61914x); EP-A 180 057; US-P 4,388,472).

Das bei Verfahren (a) weiter als Ausgangsstoff einzu­setzende 2-Amino-4-hydroxy-benzonitril der Formel (III) ist bereits bekannt (vgl. Synthesis 1985, 778 - 779).The 2-amino-4-hydroxy-benzonitrile of the formula (III) to be used further as starting material in process (a) is already known (cf. Synthesis 1985, 778-779).

Die bei den erfindungsgemäßen Verfahren (b), (c) und (d) als Ausgangsstoffe zu verwendenden Verbindungen sind durch die Formel (I) mit der Maßgabe, daß R⁶ für Amino steht, allgemein definiert. In diesem Fall haben die Reste R¹, R², R³, R⁴ und R⁵ vorzugsweise bzw. insbeson­dere diejenigen Bedeutungen, die bereits im Rahmen der Beschreibung der erfindungsgemäßen Verbindungen der For­mel (I) vorzugsweise bzw. als insbesondere bevorzugt an­gegeben wurden.The compounds to be used as starting materials in the processes (b), (c) and (d) according to the invention are generally defined by the formula (I) with the proviso that R⁶ is amino. In this case, the radicals R¹, R², R³, R⁴ and R⁵ preferably or in particular have those meanings which have already been given as preferred or as particularly preferred in the context of the description of the compounds of the formula (I) according to the invention.

Beispiele für diese Verbindungen sind Tabelle 1 (R⁶:NH₂) zu entnehmen. Diese Ausgangsstoffe sind erfindungsge­mäße, neue Verbindungen; sie können nach dem erfindungs­gemäßen Verfahren (a) hergestellt werden.Examples of these compounds can be found in Table 1 (R⁶: NH₂). These starting materials are new compounds according to the invention; they can be produced by process (a) according to the invention.

Die beim erfindungsgemäßen Verfahren (b) weiter als Aus­gangsstoffe zu verwendenden Verbindungen sind durch die Formeln (IV) und (V) allgemein definiert In diesen For­meln haben R⁹ und R¹⁰ vorzugsweise bzw. insbesondere diejenigen Bedeutungen, die bereits oben im Zusammenhang mit der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbesondere bevor­zugt für R⁹ und R¹⁰ angegeben wurden und X¹ wie auch X² stehen vorzugsweise für Fluor, Chlor oder Brom, insbe­sondere für Chlor.The compounds to be used further as starting materials in process (b) according to the invention are indicated by Formulas (IV) and (V) generally defined In these formulas, R⁹ and R¹⁰ preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R⁹ and R¹⁰ and X¹ as well as X² are preferably fluorine, chlorine or bromine, in particular chlorine.

Als Beispiele für die Ausgangsstoffe der Formeln (IV) und (V) seien genannt:
Acetylchlorid, Propionylchlorid, Butyroylchlorid, Iso­butyroylchlorid, Valeroylchlorid, Isovaleroylchlorid, Chloracetylchlorid, Dichloracetylchlorid, Trichlor­acetylchlorid, 2-Chlorpropionylchlorid, 2-Brompropionyl­chlorid, Methoxyacetylchlorid, Ethoxyacetylchlorid, 2-­Methoxypropionylchlorid, 2-Ethoxypropionylchlorid, Cyclopropancarbonsäurechlorid, Phenylacetylchlorid, Benzoylchlorid, 2-Fluor-, 4-Fluor-, 2 Chlor-, 4-Chlor-, 2-Brom-, 4-Brom-, 2-Methyl-, 2-Ethyl-, 3-Methyl-, 4-­Methyl-, 4-Ethyl-, 3-Methoxy-, 4-Methoxy- und 4-Ethoxy­benzoylchlorid, Chlorameisensäure-methylester, -ethyl­ester, -propylester und -butylester, Chlorameisensäure­phenylester, Dimethylcarbamidsäurechlorid, Methan-, Ethan-, Propan-, Butan-, Chlormethan-, Trifluormethan-, 2-Chlor-ethan- und Perfluorbutan-sulfonsäurechlorid, Benzolsulfonsäurechlorid, 2-Chlor-, 3-Chlor-, 4-Chlor-, 2,4-Dichlor-, 2,5-Dichlor-, 2-Fluor-, 4-Fluor-, 2-Brom-, 4-Brom-, 2-Methyl-, 3-Methyl-, 4-Methyl-, 2-Trifluor­methyl-, 2-Methoxy-, 4-Methoxy-, 2-Difluormethoxy-, 2-­ Trifluormethoxy-, 4-Trifluormethoxy-, 2-Dimethylamino­sulfonyl-, 2-Methoxycarbonyl- und 4-Methoxycarbonyl­benzolsulfonsäurechlorid.Examples of the starting materials of the formulas (IV) and (V) are:
Acetylchloride, propionylchloride, butyroylchloride, isobutyroylchloride, valeroylchloride, isovaleroylchloride, chloroacetylchloride, dichloroacetylchloride, trichloroacetylchloride, 2-chloropropionylchloride, 2-bromopropionylchloride, methoxyacetylchloride, ethoxyacetylchloride, 2-methoxypropylchloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride, 2-methoxypropyl chloride; -Fluoro-, 2 chloro, 4-chloro, 2-bromo, 4-bromo, 2-methyl, 2-ethyl, 3-methyl, 4-methyl, 4-ethyl, 3- Methoxy, 4-methoxy and 4-ethoxybenzoyl chloride, chloroformic acid methyl ester, ethyl ester, propyl ester and butyl ester, chloroformic acid phenyl ester, dimethyl carbamic acid chloride, methane, ethane, propane, butane, chloromethane, trifluoromethane, 2-chlorine -ethane and perfluorobutane sulfonic acid chloride, benzenesulfonic acid chloride, 2-chloro, 3-chloro, 4-chloro, 2,4-dichloro, 2,5-dichloro, 2-fluoro, 4-fluoro, 2 -Bromo, 4-bromo, 2-methyl, 3-methyl, 4-methyl, 2-trifluoromethyl, 2-methoxy, 4-methoxy -, 2-difluoromethoxy, 2- Trifluoromethoxy, 4-trifluoromethoxy, 2-dimethylaminosulfonyl, 2-methoxycarbonyl and 4-methoxycarbonylbenzenesulfonic acid chloride.

Die Ausgangsstoffe der Formel (IV) und (V) sind bekannte Verbindungen.The starting materials of the formula (IV) and (V) are known compounds.

Die bei den erfindungsgemäßen Verfahren (c) und (d) als Ausgangsstoffe zu verwendenden Acrylsäureester sind durch die Formel (VI) allgemein definiert. In Formel (VI) steht R¹² vorzugsweise für C₁-C₆-Alkyl, insbeson­dere für C₁-C₄-Alkyl.Formula (VI) provides a general definition of the acrylic acid esters to be used as starting materials in processes (c) and (d) according to the invention. In formula (VI) R¹² is preferably C₁-C₆ alkyl, especially C₁-C₄ alkyl.

Als Beispiele für die Ausgangsstoffe der Formel (VI) seien genannt:
Acrylsäure-methylester, -ethylester, -propylester und -butylester.The following may be mentioned as examples of the starting materials of the formula (VI):
Acrylic acid methyl ester, ethyl ester, propyl ester and butyl ester.

Die Verbindungen der Formel (VI) sind bekannte orga­nische Synthesechemikalien.The compounds of formula (VI) are known organic synthetic chemicals.

Die beim erfindungsgemäßen Verfahren (e) als Ausgangs­stoffe zu verwendenden Verbindungen sind durch die For­mel (I) mit der Maßgabe, daß R⁶ für die Gruppierung

Figure imgb0026
steht, allgemein definiert. In diesem Fall haben die Reste R¹, R², R³, R⁴, R⁵ und R¹² vorzugs­weise bzw. insbesondere diejenigen Bedeutungen, die be­reits im Rahmen der Beschreibung der erfindungsgemäßen Verbindungen der Formel (I) vorzugsweise bzw. als insbe­sondere bevorzugt angegeben wurden und R¹¹ steht vor­ zugsweise für Chlor oder Brom.The compounds to be used as starting materials in process (e) according to the invention are represented by the formula (I) with the proviso that R⁶ for the grouping
Figure imgb0026
 stands, generally defined. In this case, the radicals R¹, R², R³, R⁴, R⁵ and R¹² preferably or in particular have those meanings which have already been given in the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred and R¹¹ is above preferably for chlorine or bromine.

Beispiele für diese Verbindungen sind Tabelle 1 zu ent­nehmen. Diese Ausgangsstoffe sind erfindungsgemäße, neue Verbindungen; sie können nach dem erfindungsgemäßen Ver­fahren (d) hergestellt werden.Examples of these compounds can be found in Table 1. These starting materials are new compounds according to the invention; they can be prepared by process (d) according to the invention.

Das erfindungsgemäße Verfahren (a) zur Herstellung der neuen Verbindungen der Formel (I) wird vorzugsweise un­ter Verwendung von Verdünnungsmitteln durchgeführt. Als Verdünnungsmittel kommen dabei praktisch alle inerten organischen Lösungsmittel in Frage. Hierzu gehören vor­zugsweise aliphatische und aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe wie Pentan, Hexan, Hep­tan, Cyclohexan, Petrolether, Benzin, Ligroin, Benzol, Toluol, Xylol, Methylenchlorid, Ethylenchlorid, Chloro­form, Tetrachlorkohlenstoff, Chlorbenzol und o-Dichlor­benzol, Ether wie Diethyl- und Dibutylether, Glykoldime­thylether und Diglykoldimethylether, Tetrahydrofuran und Dioxan, Ketone wie Aceton, Methyl-ethyl-, Methyl-isopro­pyl- und Methyl-isobutyl-keton, Ester wie Essigsäureme­thylester und -ethylester, Nitrile wie z B. Acetonitril und Propionitril, Amide wie z B. Dimethylformamid, Di­methylacetamid und N-Methyl-pyrrolidon sowie Dimethyl­sulfoxid, Tetramethylensulfon und Hexamethylphosphor­säuretriamid.Process (a) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and Dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, amides such as bitrate Dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethyl phosphoric acid triamide.

Hiervon werden die aprotisch polaren Lösungsmittel, wie z. B. Aceton, Acetonitril, Methylethylketon, Propio­nitril, Methylisobutylketon, Methylisopropylketon, Dime­thylformamid, Dimethylacetamid, N-Methylpyrrolidon und Dimethylsulfoxid, besonders bevorzugt.Of these, the aprotic polar solvents, such as. B. acetone, acetonitrile, methyl ethyl ketone, propionitrile, methyl isobutyl ketone, methyl isopropyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide, particularly preferred.

Als Säureakzeptoren können bei dem erfindungsgemäßen Verfahren (a) alle üblicherweise für derartige Umset­zungen verwendbaren Säurebindemittel eingesetzt werden. Vorzugsweise in Frage kommen Alkalimetallhydroxide wie z. B. Natrium- und Kaliumhydroxid, Erdalkalihydroxide wie z. B. Calciumhydroxid, Alkalicarbonate und -alkoho­late wie Natrium- und Kaliumcarbonat, Natrium- und Ka­lium-tert-butylat, ferner aliphatische, aromatische oder heterocyclische Amine, beispielsweise Triethylamin, Tri­methylamin, Dimethylanilin, Dimethylbenzylamin, Pyridin, 1,5-Diazabicyclo-[4,3,0]-non-5-en (DBN), 1,8-Diazabi­cyclo-[5,4,0]-undec-7-en (DBU) und 1,4-Diazabicyclo-­[2,2,2]-octan (DABCO).Acid acceptors which can be used in process (a) according to the invention are all acid binders which can customarily be used for such reactions. Alkali metal hydroxides such as, for. B. sodium and potassium hydroxide, alkaline earth metal hydroxides such. B. calcium hydroxide, alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium and potassium tert-butoxide, also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo- [4 , 3,0] non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2 ] octane (DABCO).

Die Reaktionstemperaturen können bei dem erfindungsge­mäßen Verfahren (a) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0 °C und 200 °C, vorzugsweise bei Temperaturen zwischen 20 °C und 120 °C.The reaction temperatures in process (a) according to the invention can be varied within a substantial range. In general, temperatures between 0 ° C and 200 ° C, preferably at temperatures between 20 ° C and 120 ° C.

Das erfindungsgemäße Verfahren (a) wird im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch mög­lich, unter erhöhtem oder vermindertem Druck zu arbei­ten.Process (a) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

Zur Durchführung des erfindungsgemäßen Verfahrens (a) werden die jeweils benötigten Ausgangsstoffe im allge­meinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der beiden jeweils einge­setzten Komponenten in einem größeren Überschuß zu ver­wenden. Die Reaktionen werden im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines Säure­ akzeptors durchgeführt, und das Reaktionsgemisch wird mehrere Stunden bei der jeweils erforderlichen Tempera­tur gerührt. Die Aufarbeitung erfolgt bei dem erfin­dungsgemäßen Verfahren (a) jeweils nach üblichen Me­thoden.To carry out process (a) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent in the presence of an acid Acceptor performed, and the reaction mixture is stirred for several hours at the required temperature. Working up in process (a) according to the invention is carried out in each case by customary methods.

Das erfindungsgemäße Verfahren (b) zur Herstellung der neuen Verbindungen der Formel (I) wird gegebenenfalls unter Verwendung von Verdünnungsmitteln durchgeführt. Als Verdünnungsmittel kommen dabei alle inerten orga­nischen Lösungsmittel in Frage, wie sie oben für das er­findungsgemäße Verfahren (a) angegeben sind.Process (b) according to the invention for the preparation of the new compounds of the formula (I) is optionally carried out using diluents. Suitable diluents here are all inert organic solvents as specified above for process (a) according to the invention.

Verfahren (b) wird gegebenenfalls in Gegenwart eines Säureakzeptors durchgeführt. Als Säureakzeptoren kommen hierbei praktisch alle üblicherweise für derartige Um­setzungen verwendbaren Säurebindemittel in Frage, wie sie oben für das erfindungsgemäße Verfahren (a) angege­ben sind.Process (b) is optionally carried out in the presence of an acid acceptor. Suitable acid acceptors here are virtually all acid binders which can usually be used for such reactions, as indicated above for process (a) according to the invention.

Hiervon werden die oben genannten aliphatischen, aroma­tischen oder heterocyclischen Amine, wie z. B. Pyridin und DABCO, besonders bevorzugt.Of these, the above aliphatic, aromatic or heterocyclic amines, such as. B. pyridine and DABCO, particularly preferred.

Die Reaktionstemperaturen können bei dem erfindungsge­mäßen Verfahren (b) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20 °C und +150 °C, vorzugsweise bei Tem­peraturen zwischen 0 °C und 100 °C.The reaction temperatures can be varied within a substantial range in process (b) according to the invention. In general, temperatures between -20 ° C and +150 ° C, preferably at temperatures between 0 ° C and 100 ° C.

Das erfindungsgemäße Verfahren (b) wird im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch mög­ lich, unter erhöhtem oder vermindertem Druck zu arbei­ten.Process (b) according to the invention is generally carried out under normal pressure. However, it is also possible Lich to work under increased or reduced pressure.

Zur Durchführung des erfindungsgemäßen Verfahrens (b) werden die jeweils benötigten Ausgangsstoffe im allge­meinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der beiden jeweils einge­setzten Komponenten in einem größeren Überschuß zu ver­wenden. Die Reaktionen werden im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines Säureak­zeptors durchgeführt, und das Reaktionsgemisch wird mehrere Stunden bei der jeweils erforderlichen Tempera­tur gerührt. Die Aufarbeitung erfolgt bei dem erfin­dungsgemäßen Verfahren (b) nach üblichen Methoden.To carry out process (b) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. Working up in process (b) according to the invention is carried out by customary methods.

Das erfindungsgemäße Verfahren (c) zur Herstellung der neuen Verbindungen der Formel (I) wird vorzugsweise un­ter Verwendung von Verdünnungsmitteln durchgeführt. Als Verdünnungsmittel kommen dabei praktisch alle inerten organischen Lösungsmittel in Frage, wie sie oben für das erfindungsgemäße Verfahren (a) angegeben sind. Hiervon werden die oben angegebenen aprotisch polaren Lösungs­mittel besonders bevorzugt.Process (c) according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Practically all inert organic solvents as specified above for process (a) according to the invention are suitable as diluents. Of these, the aprotic polar solvents indicated above are particularly preferred.

Verfahren (c) wird gegebenenfalls in Gegenwart eines basischen Katalysators durchgeführt. Geeignete basische Katalysatoren sind hierbei Alkalimetall-hydroxide oder -alkoholate, wie Natrium- oder Kalium-hydroxid, -methyl­at, -ethylat oder -tert-butylat, Alkalimetallsalze von Carbonsäuren, vie z. B. Natrium- oder Kalium -acetat, sowie basische Stickstoffverbindungen, wie Diethylamin oder Piperidin.Process (c) is optionally carried out in the presence of a basic catalyst. Suitable basic catalysts are alkali metal hydroxides or alcoholates, such as sodium or potassium hydroxide, methylate, ethylate or tert-butoxide, alkali metal salts of carboxylic acids, such as. B. sodium or potassium acetate, and basic nitrogen compounds such as diethylamine or piperidine.

Die Reaktionstemperaturen können bei dem erfindungsge­mäßen Verfahren (c) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0 °C und 150 °C, vorzugsweise bei Temperaturen zwischen 20 °C und 120 °C.The reaction temperatures can be varied within a substantial range in process (c) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 20 ° C and 120 ° C.

Das erfindungsgemäße Verfahren (c) wird im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch mög­lich, unter erhöhtem oder vermindertem Druck zu arbeiten.Process (c) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

Zur Durchführung des erfindungsgemäßen Verfahrens (c) werden die jeweils benötigten Ausgangsstoffe im allge­meinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der beiden jeweils einge­setzten Komponenten in einem größeren Überschuß zu ver­wenden. Die Reaktionen werden im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines ba­sischen Katalysators durchgeführt, und das Reaktionsge­misch wird mehrere Stunden bei der jeweils erforder­lichen Temperatur gerührt. Die Aufarbeitung erfolgt bei dem erfindungsgemäßen Verfahren (c) nach üblichen Methoden.To carry out process (c) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent in the presence of a basic catalyst, and the reaction mixture is stirred for several hours at the temperature required in each case. Working up in process (c) according to the invention is carried out by customary methods.

Das erfindungsgemäße Verfahren (d) zur Herstellung von Verbindungen der Formel (I) wird unter Einsatz eines Hydrogenhalogenids (HX³) durchgeführt. Als Beispiele hierfür seien Hydrogenfluorid, Hydrogenchlorid, Hydro­genbromid und Hydrogeniodid genannt. Hydrogenchlorid und Hydrogenbromid werden vorzugsweise eingesetzt.Process (d) according to the invention for the preparation of compounds of the formula (I) is carried out using a hydrogen halide (HX 3). Examples of these are hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide. Hydrogen chloride and hydrogen bromide are preferably used.

Verfahren (d) wird vorzugsweise unter Verwendung eines organischen Lösungsmittels durchgeführt. Insbesondere geeignet sind Ether, wie z B. Glycoldimethylether und Diglycoldimethylether, Tetrahydrofuran und Dioxan, Ke­tone, wie z. B. Aceton und Methylethylketon, sowie Amide wie z. B. Dimethylformamid.Process (d) is preferably carried out using an organic solvent. Particularly suitable are ethers, such as glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as. B. acetone and methyl ethyl ketone, and amides such as. B. Dimethylformamide.

Verfahren (d) wird weiter vorzugsweise in Gegenwart von Katalysatoren duchgeführt. Als solche kommen insbeson­dere Kupfer und Kupferverbindungen, wie z. B. Kupfer(I)-­chlorid, Kupfer(II)-chlorid, Kupfer(I)-bromid, Kupfer­(I)-iodid, Kupfer(II)-sulfat und Kupfer(II)-nitrat in Betracht.Process (d) is further preferably carried out in the presence of catalysts. As such come in particular copper and copper compounds such. B. copper (I) chloride, copper (II) chloride, copper (I) bromide, copper (I) iodide, copper (II) sulfate and copper (II) nitrate into consideration.

Die Reaktionstemperaturen können bei dem erfindungsge­mäßen Verfahren (d) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20 °C und +80 °C, vorzugsweise bei Tempera­turen zwischen 0 °C und 60 °C.The reaction temperatures can be varied within a substantial range in process (d) according to the invention. In general, temperatures between -20 ° C and +80 ° C, preferably at temperatures between 0 ° C and 60 ° C.

Verfahren (d) wird im allgemeinen bei Normaldruck durch­geführt.Process (d) is generally carried out under normal pressure.

Zur Durchführung des erfindungsgemäßen Verfahrens (d) setzt man je Mol Phenoxyphenylaminoverbindung der Formel (I) im allgemeinen zwischen 0,8 und 2,5 Mol, vorzugs­weise zwischen 1,1 und 2,0 Mol, Natriumnitrit oder Ka­liumnitrit, zwischen 2 und 50 Mol, vorzugsweise zwischen 5 und 25 Mol, Hydrogenhalogenid, und zwischen 1 und 3 Mol, vorzugsweise zwischen 1,5 und 2,5 Mol, Acrylsäure-­Derivat der Formel (VI) ein.To carry out process (d) according to the invention, generally between 0.8 and 2.5 mol, preferably between 1.1 and 2.0 mol, sodium nitrite or potassium nitrite, between 2 and 50 mol are used per mol of phenoxyphenylamino compound of the formula (I) , preferably between 5 and 25 mol, hydrogen halide, and between 1 and 3 mol, preferably between 1.5 and 2.5 mol, acrylic acid derivative of the formula (VI).

Verfahren (d) kann unter den üblichen Bedingungen der "Meerwein-Arylierung" durchgeführt werden. In einer be­vorzugten Ausführungsform von Verfahren (d) wird zu­nächst die Ausgangsverbindung der Formel (I) in einem Verdünnungsmittel, welches zumindest Wasser und ein Hy­drogenhalogenid enthält, verrührt und unter Kühlen mit einer wäßrigen Lösung von Natriumnitrit oder Kaliumni­trit diazotiert. Dann wird das Acrylsäure-Derivat der Formel (VI) und gegebenenfalls der Katalysator zum Reak­tionsgemisch gegeben. Wenn - gegebenenfalls nach leich­tem Erwärmen - die Stickstoff-Entwicklung abgeklungen ist, kann nach üblichen Methoden aufgearbeitet werden.Process (d) can be carried out under the usual conditions of "sea wine arylation". In a preferred embodiment of process (d), the starting compound of the formula (I) is first stirred in a diluent which comprises at least water and a hydrogen halide and diazotized with cooling with an aqueous solution of sodium nitrite or potassium nitrite. Then the acrylic acid derivative of the formula (VI) and optionally the catalyst are added to the reaction mixture. When - if necessary after gentle warming - the nitrogen evolution has subsided, it can be worked up using customary methods.

Das erfindungsgemäße Verfahren (e) zur Herstellung von Verbindungen der Formel (I) wird unter Einsatz eines De­halogenierungsmittels durchgeführt. Es können hierbei die üblichen zur Dehalogenierung geeigneten Substanzen, wie z. B. Tributylzinnhydrid, verwendet werden.Process (e) according to the invention for the preparation of compounds of the formula (I) is carried out using a dehalogenating agent. It can be the usual substances suitable for dehalogenation, such as. B. tributyltin hydride can be used.

Verfahren (e) wird gegebenenfalls in Gegenwart eines Katalysators durchgeführt. Als Katalysatoren kommen hierbei als Radikalstarter gebräuchliche Substanzen, wie z. B. Azo-bis-isobutyronitril, in Betracht.Process (e) is optionally carried out in the presence of a catalyst. As catalysts here come as free radical initiators, such as. B. azo-bis-isobutyronitrile, into consideration.

Verfahren (e) wird vorzugsweise in Gegenwart eines Ver­dünnungsmittels durchgeführt. Als Verdünnungsmittel kom­men dabei praktisch alle inerten organischen Lösungsmit­tel in Frage. Hierzu gehören vorzugsweise aliphatische und aromatische, gegebenenfalls halogenierte Kohlenwas­serstoffe, wie Pentan, Hexan, Heptan, Cyclohexan, Me­thylcyclohexan, Benzol, Toluol, Xylol, Chlorbenzol und o-Dichlorbenzol, sowie Ether, wie Diethylether, Dipro­ pylether, Diisopropylether, Dibutylether, Diisobutyl­ether, Glycoldimethylether, Diglycoldimethylether, Tetrahydrofuran und Dioxan.Process (e) is preferably carried out in the presence of a diluent. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, chlorobenzene and o-dichlorobenzene, and ethers, such as diethyl ether, dipro pyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran and dioxane.

Die Reaktionstemperaturen können bei dem erfindungsge­mäßen Verfahren (e) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0 °C und 150 °C, vorzugsweise bei Temperaturen zwischen 10 °C und 100 °C.The reaction temperatures can be varied within a substantial range in process (e) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably at temperatures between 10 ° C and 100 ° C.

Das erfindungsgemäße Verfahren (e) wird im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch mög­lich, unter erhöhtem oder vermindertem Druck zu arbeiten.Process (e) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.

Zur Durchführung des erfindungsgemäßen Verfahrens (e) werden die jeweils benötigten Ausgangsstoffe im allge­meinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der beiden jeweils einge­setzten Komponenten in einem größeren Überschuß zu ver­wenden. Die Reaktionen werden im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines Kataly­sators durchgeführt, und das Reaktionsgemisch wird mehrere Stunden bei der jeweils erforderlichen Tempera­tur gerührt. Die Aufarbeitung erfolgt bei dem erfin­dungsgemäßen Verfahren (e) jeweils nach üblichen Me­thoden.To carry out process (e) according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent in the presence of a catalyst and the reaction mixture is stirred for several hours at the temperature required in each case. Working up in process (e) according to the invention is carried out in each case by customary methods.

Die erfindungsgemäßen Wirkstoffe können als Defoliants, Desiccants, Krautabtötungsmittel und insbesondere als Unkrautvernichtungsmittel verwendet werden. Unter Un­kraut im weitesten Sinne sind alle Pflanzen zu verste­ hen, die an Orten aufwachsen, wo sie unerwünscht sind. Ob die erfindungsgemäßen Stoffe als totale oder selek­tive Herbizide wirken, hängt im wesentlichen von der an­gewendeten Menge ab.The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants hen who grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

Die erfindungsgemäßen Wirkstoffe können z.B. bei den folgenden Pflanzen verwendet werden:
Dikotyle Unkräuter der Gattungen: Sinapis, Lepidium, Ga­lium, Stellaria, Matricaria, Anthemis, Galinsoga, Cheno­podium, Urtica, Senecio, Amaranthus, Portulaca, Xanthi­um, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
Dikotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lac­tuca, Cucumis, Cucurbita.
Monokotyle Unkräuter der Gattungen: Echinochloa, Seta­ria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagitta­ria, Eleocharis, Scirpus, Paspalum, Ischaemum, Spheno­clea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monokotyle Kulturen der Gattungen: Oryza Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.The active compounds according to the invention can be used, for example, in the following plants:
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduippum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasemirumum, Scalumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocot cultures of the genera: Oryza Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

Die Verwendung der erfindungsgemäßen Wirkstoffe ist je­doch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflan­zen.However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Die Verbindungen eignen sich in Abhängigkeit von der Konzentration zur Totalunkrautbekämpfung z.B. auf In­dustrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen, z.B. Forst, Zierge­hölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht- und Hopfen­anlagen und zur selektiven Unkrautbekämpfung in ein­jährigen Kulturen eingesetzt werden.Depending on the concentration, the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, e.g. Forests, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annual crops.

Die erfindungsgemäßen Verbindungen eignen sich insbe­sondere zur selektiven Bekämpfung von dikotylen Unkräu­tern in monokotylen Kulturen, vor allem im Nachlauf-Ver­fahren.The compounds according to the invention are particularly suitable for the selective control of dicotyledon weeds in monocotyledon crops, especially in the wake process.

Die erfindungsgemäßen Wirkstoffe greifen in den Metabo­lismus der Pflanzen ein und können deshalb als Wachs­tumsregulatoren eingesetzt werden.The active compounds according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators.

Für die Wirkungsweise von Pflanzenwachstumsregulatoren gilt nach der bisherigen Erfahrung, daß ein Wirkstoff auch mehrere verschiedenartige Wirkungen auf Pflanzen ausüben kann. Die Wirkungen der Stoffe hängen im wesent­lichen ab von dem Zeitpunkt der Anwendung bezogen auf das Entwicklungsstadium der Pflanze sowie von den auf die Pflanzen oder ihre Umgebung ausgebrachten Wirkstoff­mengen und von der Art der Applikation. In jedem Fall sollen Wachstumsregulatoren die Kulturpflanzen in be­stimmter gewünschter Weise beeinflussen.According to previous experience, the principle of action of plant growth regulators is that an active ingredient can also have several different effects on plants. The effects of the substances essentially depend on the point in time of use, based on the stage of development of the plant, on the amounts of active ingredient applied to the plants or their environment and on the type of application. In any case growth regulators are intended to influence the crop plants in a desired manner.

Unter dem Einfluß von Wachstumsregulatoren kann der Blattbestand der Pflanzen so gesteuert werden, daß ein Entblättern der Pflanzen zu einem gewünschten Zeitpunkt erreicht wird Eine derartige Entlaubung spielt bei der mechanischen Beerntung der Baumwolle eine große Rolle ist aber auch in anderen Kulturen wie z.B. im Weinbau zur Erleichterung der Ernte von Interesse. Eine Entlau­bung der Pflanzen kann auch vorgenommen werden, um die Transpiration der Pflanzen vor dem Verpflanzen herabzu­setzen.Under the influence of growth regulators, the amount of leaves in the plants can be controlled in such a way that defoliation of the plants is achieved at a desired point in time. Such defoliation plays a large role in the mechanical harvesting of cotton, but is also important in other crops, such as e.g. of interest in viticulture to facilitate harvesting. Defoliation of the plants can also be carried out in order to reduce the transpiration of the plants before transplanting.

Die Wirkstoffe können in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Spritzpul­ver, Suspensionen, Pulver, Stäubemittel, Pasten, lös­liche Pulver, Granulate, Suspensions-Emulsions-Konzen­trate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen.The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.

Diese Formulierungen werden in bekannter Weise herge­stellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln.These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

Im Falle der Benutzung von Wasser als Streckmittel kön­nen z.B. auch organische Lösungsmittel als Hilfslösungs­mittel verwendet werden. Als flüssige Lösungsmittel kom­ men im wesentlichen in Frage: Aromaten, wie Xylol, Tolu­ol oder Alkylnaphthaline, chlorierte Aromaten und chlo­rierte aliphatische Kohlenwasserstoffe, wie Chlorbenzo­le, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alko­hole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methylisobu­tylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser.If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Com as liquid solvent Men essentially in question: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or Glycol and its ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Als feste Trägerstoffe kommen in Frage:
z.B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Ge­steinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kom­men in Frage: z.B. gebrochene und fraktionierte natürli­che Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolo­mit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Mate­rial wie Sägemehl, Kokosnußschalen, Maiskolben und Taba­kstengeln; als Emulgier- und/oder schaumerzeugende Mit­tel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Poly­oxyethylen-Fettalkohol-Ether, z.B. Alkylaryl-polyglykol­ether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.The following are suitable as solid carriers:
e.g. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granulates are possible: e.g. broken and fractionated natural rocks such as Calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.

Es können in den Formulierungen Haftmittel wie Carboxy­ methylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipide, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein.Adhesives such as carboxy can be used in the formulations methyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farb­stoffe, wie Alizarin-, Azo- und Metallphthalocyaninfarb­stoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden.Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Herbiziden zur Unkrautbekämpfung Verwendung finden, wo­bei Fertigformulierungen oder Tankmischungen möglich sind.The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known herbicides for weed control, finished formulations or tank mixes being possible.

Für die Mischungen kommen bekannte Herbizide wie z.B. 1-­Amino-6-ethylthio-3-(2,2-dimethylpropyl )-1 ,3,5-triazin-­2,4(1H,3H)-dion (AMETHYDIONE) oder N-(2-Benzthiazolyl)-­N,N′-dimethyl-harnstoff (METABENZTHIAZURON) zur Unkraut­bekämpfung in Getreide; 4-Amino-3-methyl-6-phenyl-1,2,4-­triazin-5(4H)-on (METAMITRON) zur Unkrautbekämpfung in Zuckerrüben und 4-Amino-6-(1,1-dimethylethyl)-3-methyl­thio-1,2,4-triazin-5(4H)-on (METRIBUZIN) zur Unkraut­bekämpfung in Sojabohnen, in Frage; ferner auch 2,4-Di­ chlorphenoxyessigsäure (2,4-D); 4-(2,4-Dichlorphenoxy)-­buttersäure (2,4-DB); 2,4-Dichlorphenoxypropionsäure (2,4-DP); 3-Isopropyl-2,1,3-benzothiadiazin-4-on2,2-­dioxid (BENTAZON); 3,5-Dibrom-4-hydroxy-benzonitril (BROMOXYNIL); 2-Chlor-N-{[(4-methoxy-6-methyl-1,3,5-­triazin-2-yl)-amino]-carbonyl}-benzolsulfonamid (CHLOR­SULFURON); N,N-Dimethyl-N′-(3-chlor-4-methylphenyl)-­harnstoff (CHLORTOLURON); 2-[4-(2,4-Dichlorphenoxy)-­phenoxy]-propionsäure, deren Methyl- oder deren Ethyl­ester (DICLOFOP); 4-Amino-6-t-butyl-3-ethylthio-1,2,4-­triazin-5(4H)-on (ETHIOZIN); 2-{4-[(6-Chlor-2-benzox­azolyl)-oxy]-phenoxy}-propansäure, deren Methyl- oder deren Ethylester (FENOXAPROP); [(4-Amino-3,5-dichlor-6-­fluor-2-pyridinyl)-oxy]-essigsäure bzw. deren 1-Methyl­heptylester (FLUROXYPYR); N-Phosphonomethyl-glycin (GLY­PHOSATE); Methyl-2-[4,5-dihydro-4-methyl-4-(1-methyl­ethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoat (IM­AZAMETHABENZ); 3,5-Diiod-4-hydroxybenzonitril (IOXYNIL); N,N-Dimethyl-N′-(4-isopropylphenyl)-harnstoff (ISOPROTU­RON); (2-Methyl-4-chlorphenoxy)-essigsäure (MCPA); (4-­Chlor-2-methylphenoxy)-propionsäure (MCPP); N-Methyl-2-­(1,3-benzthiazol-2-yloxy)-acetanilid (MEFENACET); 2-­{[[((4-Methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-­carbonyl]-amino]-sulfonyl}-benzoesäure oder deren Me­thylester (METSULFURON); N-(1-Ethylpropyl)-3,4-dimethyl-­2,6-dinitroanilin (PENDIMETHALIN); 4-Ethylamino-2-t-bu­tylamino-6-methylthio-s-triazin (TERBUTRYNE); 3-[[[[(4-­Methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-­amino]-sulfonyl]-thiophen-2-carbonsäure-methylester (THIAMETURON); Einige Mischungen zeigen überraschender­weise auch synergistische Wirkung.Known herbicides such as 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1, 3,5-triazine-2,4 (1H, 3H) -dione (AMETHYDIONE) or N- (2-benzothiazolyl) -N, N'-dimethyl-urea (METABENZTHIAZURON) for weed control in cereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one (METAMITRON) for weed control in sugar beets and 4-amino-6- (1,1-dimethylethyl) -3- methylthio-1,2,4-triazin-5 (4H) -one (METRIBUZIN) for weed control in soybeans, in question; also 2,4-Di chlorophenoxyacetic acid (2,4-D); 4- (2,4-dichlorophenoxy) butyric acid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP); 3-isopropyl-2,1,3-benzothiadiazin-4-one2,2-dioxide (BENTAZON); 3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL); 2-chloro-N - {[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl} benzenesulfonamide (CHLORSULFURON); N, N-dimethyl-N ′ - (3-chloro-4-methylphenyl) urea (CHLORTOLURON); 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid, its methyl or its ethyl ester (DICLOFOP); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5 (4H) -one (ETHIOZIN); 2- {4 - [(6-chloro-2-benzoxazolyl) -oxy] -phenoxy} -propanoic acid, its methyl or its ethyl ester (FENOXAPROP); [(4-Amino-3,5-dichloro-6-fluoro-2-pyridinyl) -oxy] acetic acid or its 1-methylheptyl ester (FLUROXYPYR); N-phosphonomethyl-glycine (GLYPHOSATE); Methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -4 (5) methylbenzoate (IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL); N, N-Dimethyl-N ′ - (4-isopropylphenyl) urea (ISOPROTURON); (2-methyl-4-chlorophenoxy) acetic acid (MCPA); (4-chloro-2-methylphenoxy) propionic acid (MCPP); N-methyl-2- (1,3-benzothiazol-2-yloxy) acetanilide (MEFENACET); 2 - {[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino) carbonyl] amino] sulfonyl} benzoic acid or its methyl ester (METSULFURON); N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALINE); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); 3 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] thiophene-2-carboxylic acid methyl ester (THIAMETURON) ; Surprisingly, some mixtures also show a synergistic effect.

Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Pflanzennährstoffen und Bodenstrukturverbesserungsmitteln ist möglich.A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

Die Wirkstoffe können als solche, in Form ihrer Formu­lierungen oder den daraus durch weiteres Verdünnen be­reiteten Anwendungsformen, wie gebrauchsfertige Lösun­gen, Suspensionen, Emulsionen, Pulver, Pasten und Granu­late angewandt werden. Die Anwendung geschieht in üb­licher Weise, z.B. durch Gießen, Spritzen, Sprühen, Streuen.The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.

Die erfindungsgemäßen Wirkstoffe können sowohl vor als auch nach dem Auflaufen der Pflanzen appliziert werden.The active compounds according to the invention can be applied both before and after emergence of the plants.

Sie können auch vor der Saat in den Boden eingearbeitet werden.They can also be worked into the soil before sowing.

Die angewandte Wirkstoffmenge kann in einem größeren Be­reich schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effektes ab. Im allgemeinen liegen die Aufwandmengen zwischen 0,01 und 10 kg Wirkstoff pro Hek­tar Bodenfläche, vorzugsweise zwischen 0,05 und 5 kg pro ha.The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor.The preparation and use of the active compounds according to the invention can be seen from the examples below.

Herstellungsbeispiele:Manufacturing examples: Beispiel 1example 1

Figure imgb0027
Figure imgb0027

13,4 g (0,1 Mol) 2-Amino-4-hydroxy-benzonitril werden in 200 ml Dimethylsulfoxid vorgelegt und nach Zugabe von 4,0 g (0,1 Mol) Natriumhydroxid wird das Gemisch 30 Minuten bei 50 °C gerührt. Anschließend wird eine Lösung von 24,9 g (0,1 Mol) 3,4,5-Trichlor-benzotrifluorid in 100 ml Dimethylsulfoxid bei 50 °C unter Rühren tropfen­weise dazugegeben. Dann wird das Reaktionsgemisch noch 5 Stunden bei 50 °C und weitere 2 Stunden bei 90 °C ge­rührt, nach Abkühlen in 1 l Wasser gegossen und das Pro­dukt mit Chloroform extrahiert. Die organische Phase wird mit Magnesiumsulfat getrocknet und filtriert. Vom Filtrat wird das Lösungsmittel im Wasserstrahlvakuum sorgfältig abdestilliert.13.4 g (0.1 mol) of 2-amino-4-hydroxy-benzonitrile are placed in 200 ml of dimethyl sulfoxide and after adding 4.0 g (0.1 mol) of sodium hydroxide, the mixture is stirred at 50 ° C. for 30 minutes . A solution of 24.9 g (0.1 mol) of 3,4,5-trichlorobenzotrifluoride in 100 ml of dimethyl sulfoxide is then added dropwise at 50 ° C. while stirring. The reaction mixture is then stirred for a further 5 hours at 50 ° C. and for a further 2 hours at 90 ° C., after cooling, poured into 1 liter of water and the product is extracted with chloroform. The organic phase is dried with magnesium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum.

Man erhält 29,5 g (85 % der Theorie) 2-Amino-4-(2,6-di­chor-4-trifluormethyl-phenoxy)-benzonitril als amorphen Rückstand.

Figure imgb0028
29.5 g (85% of theory) of 2-amino-4- (2,6-dichor-4-trifluoromethyl-phenoxy) -benzonitrile are obtained as an amorphous residue.
Figure imgb0028

Beispiel 2Example 2

Figure imgb0029
Figure imgb0029

Eine Mischung aus 3,47g (0,01 Mol) 2-Amino-4-(2,6-di­chlor-4-trifluormethyl-phenoxy)-benzonitril, 10 ml Me­thansulfonsäurechlorid und 1 g Pyridin wird 15 Stunden bei 60 °C gerührt. Dann wird die Reaktionsmischung in 50 ml Wasser gegossen und das Produkt mit Chloroform extrahiert. Die organische Phase wird mit Magnesiumsul­fat getrocknet und filtriert. Vom Filtrat wird das Lö­sungsmittel im Wasserstrahlvakuum abdestilliert und der Rückstand durch Säulenchromatographie (Kieselgel; Hexan/Essigsäureethylester 4 : 1) gereinigt. Man erhält 2,2 g (52 % der Theorie) 2-Methylsulfonylamino-4-(2,6-­ dichlor-4-trifluormethyl-phenoxy)-benzonitril als amorphes Produkt.

Figure imgb0030
A mixture of 3.47 g (0.01 mol) of 2-amino-4- (2,6-dichloro-4-trifluoromethylphenoxy) benzonitrile, 10 ml of methanesulfonic acid chloride and 1 g of pyridine is stirred at 60 ° C. for 15 hours. Then the reaction mixture is poured into 50 ml of water and the product extracted with chloroform. The organic phase is dried with magnesium sulfate and filtered. The solvent is distilled off from the filtrate in a water jet vacuum and the residue is purified by column chromatography (silica gel; hexane / ethyl acetate 4: 1). 2.2 g (52% of theory) of 2-methylsulfonylamino-4- (2,6- dichloro-4-trifluoromethyl-phenoxy) benzonitrile as an amorphous product.
Figure imgb0030

Beispiel 3Example 3

Figure imgb0031
Figure imgb0031

Eine Mischung aus 4,16 g (0,012 Mol) 2-Amino-4-(2,6-di­chlor-4-trifluormethyl-phenoxy)-benzonitril, 0,3 g Na­triumacetat, 1,03 g (0,012 Mol) Acrylsäuremethylester und 100 ml Dimethylsulfoxid wird 8 Stunden bei 100 °C gerührt und dann in 300 ml Wasser gegossen. Das Produkt wird mit Chloroform extrahiert, die organische Phase mit Magnesiumsulfat getrocknet und filtriert Vom Filtrat wird das Lösungsmittel im Wasserstrahlvakuum abdestil­liert und der Rückstand durch Säulenchromatographie (Kieselgel; Ether/Petrolether 1 : 2) gereinigt. Man er­hält 0,62 g (12 % der Theorie) 2-(2-Methoxycarbonyl­ethylamino)-4-(2,6-dichlor-4-trifluormethyl-phenoxy)-­benzonitril als amorphes Produkt.

Figure imgb0032
A mixture of 4.16 g (0.012 mol) of 2-amino-4- (2,6-dichloro-4-trifluoromethylphenoxy) benzonitrile, 0.3 g of sodium acetate, 1.03 g (0.012 mol) of methyl acrylate and 100 ml of dimethyl sulfoxide is stirred for 8 hours at 100 ° C. and then poured into 300 ml of water. The product is extracted with chloroform, the organic phase is dried with magnesium sulfate and filtered. From the filtrate the solvent is distilled off in a water jet vacuum and the residue is purified by column chromatography (silica gel; ether / petroleum ether 1: 2). 0.62 g (12% of theory) of 2- (2-methoxycarbonylethylamino) -4- (2,6-dichloro-4-trifluoromethylphenoxy) benzonitrile is obtained as an amorphous product.
Figure imgb0032

Beispiel 4Example 4

Figure imgb0033
Figure imgb0033

Zu 6,9 g (0,02 Mol) 2-Amino-4-(2,6-dichlor-4-trifluor­methyl-phenoxy)-benzonitril in 200 ml Aceton gibt man 50 ml 18%ige Salzsäure und anschließend tropfenweise un­ter Rühren und Kühlen auf 0 °C bis 5 °C eine Lösung von 2,0 g (0,03 Mol) Natriumnitrit in 10 ml Wasser. Das Reaktionsgemisch wird 30 Minuten bei 0 °C bis 5 °C ge­rührt und anschließend werden 8,6 g (0,1 Mol) Acryl­ säuremethylester und eine Lösung von 2 g (0,02 Mol) Kupfer(I)-chlorid in 5 ml konzentrierter Salzsäure dazu­gegeben. Nach 2 Stunden Rühren bei 5 °C wird mit 200 ml Wasser verdünnt, das Produkt mit Chloroform extrahiert, die organische Phase mit Magnesiumsulfat getrocknet und filtriert. Vom Filtrat wird das Lösungsmittel im Wasser­strahlvakuum abdestilliert und der Rückstand durch Säu­lenchromatographie (Kieselgel, Hexan/Essigsäureethyl­ester 4 : 1) gereinigt.50 ml of 18% hydrochloric acid are added to 6.9 g (0.02 mol) of 2-amino-4- (2,6-dichloro-4-trifluoromethyl-phenoxy) benzonitrile in 200 ml of acetone and then added dropwise with stirring and Cool to 0 ° C to 5 ° C a solution of 2.0 g (0.03 mol) sodium nitrite in 10 ml water. The reaction mixture is stirred for 30 minutes at 0 ° C to 5 ° C and then 8.6 g (0.1 mol) of acrylic acid methyl ester and a solution of 2 g (0.02 mol) of copper (I) chloride in 5 ml of concentrated hydrochloric acid. After stirring at 5 ° C. for 2 hours, the mixture is diluted with 200 ml of water, the product is extracted with chloroform, the organic phase is dried with magnesium sulfate and filtered. The solvent is distilled off from the filtrate in a water jet vacuum and the residue is purified by column chromatography (silica gel, hexane / ethyl acetate 4: 1).

Man erhält 3,8 g (42 % der Theorie) 2-(2-Chlor-2-me­thoxycarbonyl-ethyl)-4-(2,6-dichlor-4-trifluormethyl­phenoxy)-benzonitril als amorphes Produkt.

Figure imgb0034
3.8 g (42% of theory) of 2- (2-chloro-2-methoxycarbonyl-ethyl) -4- (2,6-dichloro-4-trifluoromethylphenoxy) benzonitrile are obtained as an amorphous product.
Figure imgb0034

Beispiel 5Example 5

Figure imgb0035
Figure imgb0035

3,0 g (0,0069 Mol) 2-(2-Chlor-2-methoxycarbonylethyl)-4-­(2,6-dichlor-4-trifluormethyl-phenoxy)-benzonitril wer­den in 50 ml Toluol gelöst und 2,0 g (0,0069 Mol) Tri­butylzinnhydrid werden dazu gegeben. Nach Zugabe von 0,5 g Azo-bis-isobutyronitril wird das Reaktionsgemisch 10 Stunden bei 60 °C gerührt. Dann wird das Lösungsmit­tel im Wasserstrahlvakuum abdestilliert und der Rück­stand durch Säulenchromatographie (Kieselgel, Methylen­chlorid) gereinigt.3.0 g (0.0069 mol) of 2- (2-chloro-2-methoxycarbonylethyl) -4- (2,6-dichloro-4-trifluoromethylphenoxy) benzonitrile are dissolved in 50 ml of toluene and 2.0 g (0.0069 mol) tributyltin hydride are added. After adding 0.5 g of azo-bis-isobutyronitrile, the reaction mixture is stirred at 60 ° C. for 10 hours. Then the solvent is distilled off in a water jet vacuum and the residue is purified by column chromatography (silica gel, methylene chloride).

Man erhält 1,3 g (43 % der Theorie) 2-(2-Methoxycar­bonyl-ethyl)-4-(2,6-dichlor-4-trifluormethyl-phenoxy)-­benzonitril als amorphes Produkt.

Figure imgb0036
1.3 g (43% of theory) of 2- (2-methoxycarbonyl-ethyl) -4- (2,6-dichloro-4-trifluoromethylphenoxy) benzonitrile are obtained as an amorphous product.
Figure imgb0036

Analog zu den Beispielen 1 bis 5 und entsprechend der allgemeinen Beschreibung der erfindungsgemäßen Verfah­ren können die in der nachstehenden Tabelle 2 aufgeführ­ten Verbindungen der Formel (I) hergestellt werden.

Figure imgb0037
Figure imgb0038
 Analogously to Examples 1 to 5 and in accordance with the general description of the processes according to the invention, the compounds of the formula (I) listed in Table 2 below can be prepared.
Figure imgb0037
Figure imgb0038

AnwendungsbeispieleExamples of use

In den folgenden Anwendungsbeispielen wird die nach­stehend aufgeführte Verbindung als Vergleichssubstanz herangezogen:

Figure imgb0039
In the following application examples, the compound listed below is used as a reference substance:
Figure imgb0039

Beispiel AExample A Post-emergence-TestPost emergence test

Lösungsmittel: 5 Gewichtsteile AcetonSolvent: 5 parts by weight of acetone

Emulgator: 1 Gewichtsteil AlkylarylpolyglykoletherEmulsifier: 1 part by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmäßigen Wirkstoffzübereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebe­nen Menge Lösungsmittel, gibt die angegebene Menge Emul­gator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Mit der Wirkstoffzubereitung spritzt man Testpflanzen, welche eine Höhe von 5 - 15 cm haben so, daß die jeweils gewünschten Wirkstoffmengen pro Flächeneinheit ausge­bracht werden. Die Konzentration der Spritzbrühe wird so gewählt, daß in 2000 l Wasser/ha die jeweils gewünschten Wirkstoffmengen ausgebracht werden. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandel­ten Kontrolle.
Es bedeuten:
0 % = keine Wirkung (wie unbehandelte Kontrolle)
100 % = totale VernichtungTest plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 2000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
It means:
0% = no effect (like untreated control)
100% = total annihilation

In diesem Test zeigen beispielsweise die Verbindungen gemäß den Herstellungsbeispielen (2) und (4) erheblich stärkere Wirkung als die bekannte Verbindung (A) gegen Unkräuter, wie z. B. Ipomoea, Sida, Sinapis und Viola.In this test, for example, the compounds according to preparation examples (2) and (4) show considerably stronger activity than the known compound (A) against weeds, such as. B. Ipomoea, Sida, Sinapis and Viola.

Beispiel BExample B Entlaubung und Austrocknung der Blätter bei BaumwolleDefoliation and drying of the leaves of cotton

Lösungsmittel: 30 Gewichtsteile DimethylformamidSolvent: 30 parts by weight of dimethylformamide

Emulgator: 1 Gewichtsteil Polyoxyethylen-Sorbitan-­MonolauratEmulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebe­nen Mengen Lösungsmittel und Emulgator und füllt mit Wasser auf die gewünschte Konzentration auf.To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the mixture is made up to the desired concentration with water.

Baumwollpflanzen werden im Gewächshaus bis zur vollen Entfaltung des 5. Folgeblattes angezogen. In diesem Sta­dium werden die Pflanzen tropfnaß mit den Wirkstoffzube­reitungen besprüht. Nach 1 Woche werden der Blattfall und das Austrocknen der Blätter im Vergleich zu den Kon­trollpflanzen bonitiert.Cotton plants are grown in the greenhouse until the 5th following leaf is fully developed. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 1 week, the leaf fall and the drying out of the leaves are rated in comparison to the control plants.

In diesem Test zeigen beispielsweise die Wirkstoffe ge­mäß den Herstellungsbeispielen (3) und (4) ein sehr starkes Austrocknen der Blätter und sehr starken Blatt­fall.In this test, for example, the active ingredients according to the preparation examples (3) and (4) show very strong drying out of the leaves and very strong falling of the leaves.

Claims (8)

1. Substituierte Phenoxybenzonitril-Derivate der Formel (I),
Figure imgb0040
 in welcher
R¹ für Wasserstoff, Halogen, Cyano oder Trifluormethyl steht,
R² für Wasserstoff oder Halogen steht,
R³ für Halogen, Trifluormethyl, Trifluormethoxy oder Trifluormethylsulfonyl steht,
R⁴ für Wasserstoff oder Halogen steht,
R⁵ für Wasserstoff oder Halogen steht und
R⁶ für die Gruppierungen
Figure imgb0041
 oder
Figure imgb0042
 steht, worin
R⁷ und R⁸ gleich oder verschieden sind und unabhängig voneinander jeweils für Wasserstoff, Alkoxycarbonylethyl, die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ stehen, wobei
R⁹ für jeweils gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cyclo­alkylalkyl, Benzyl, Phenyl, Naphthyl, Pyridyl, Furyl, Thienyl, Alkoxy, Phenoxy, Alkylthio, Phenylthio, Alkylamino, Dialkylamino, Cyclo­alkylamino oder Phenylamino steht und
R¹⁰ für jeweils gegebenenfalls substituiertes Alkyl, Phenyl, Naphthyl, Pyridyl oder Thienyl steht,
R¹¹ für Wasserstoff oder Halogen steht und
R¹² für Alkyl steht.1. Substituted phenoxybenzonitrile derivatives of the formula (I),
Figure imgb0040
 in which
R¹ represents hydrogen, halogen, cyano or trifluoromethyl,
R² represents hydrogen or halogen,
R³ represents halogen, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl,
R⁴ represents hydrogen or halogen,
R⁵ represents hydrogen or halogen and
R⁶ for the groupings
Figure imgb0041
 or
Figure imgb0042
 stands in what
R⁷ and R⁸ are the same or different and each independently represent hydrogen, alkoxycarbonylethyl, the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, where
R⁹ represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, benzyl, phenyl, naphthyl, pyridyl, furyl, thienyl, alkoxy, phenoxy, alkylthio, phenylthio, alkylamino, dialkylamino, cycloalkylamino or phenylamino and
R¹⁰ represents optionally substituted alkyl, phenyl, naphthyl, pyridyl or thienyl,
R¹¹ represents hydrogen or halogen and
R¹² is alkyl. 2. Substituierte Phenoxybenzonitril-Derivate der Formel (I) gemäß Anspruch 1, in welcher
R¹ für Wasserstoff, Fluor, Chlor, Brom, Cyano oder Trifluormethyl steht,
R² für Wasserstoff, Fluor oder Chlor steht,
R³ für Fluor, Chlor, Brom, Trifluormethyl, Trifluormethoxy oder Trifluormethylsulfonyl steht,
R⁴ für Wasserstoff, Fluor oder Chlor steht,
R⁵ für Wasserstoff, Fluor oder Chlor steht und
R⁶ für die Gruppierungen
Figure imgb0043
 oder
Figure imgb0044
 steht, worin
R⁷ und R⁸ gleich oder verschieden sind und unabhängig voneinander jeweils für Was­serstoff, C₁-C₆-Alkoxy-carbonyl-ethyl, die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ stehen, wobei
R⁹ für gegebenenfalls durch Fluor, Chlor, Brom, C₁-C₄-Alkoxy und/oder C₁-C₄-Alkoxy-carbonyl substituiertes C₁-C₆-Alkyl, für gegebenenfalls durch Fluor, Chlor und/oder Brom substitu­iertes C₂-C₄-Alkenyl, für C₂-C₄-Alkinyl, für gegebenenfalls durch Fluor, Chlor, Brom, C₁-­C₄-Alkyl und/oder C₁-C₄-Alkoxy-carbonyl substituiertes C₃-C₆-Cycloalkyl, für ge­gebenenfalls durch Fluor, Chlor, Brom und/oder C₁-C₄-Alkyl substituiertes C₃-C₆-Cycloalkyl-­C₁-C₂-alkyl, für gegebenenfalls durch Fluor, Chlor, Brom, C₁-C₄-Alkyl und/oder C₁-C₄-Alkoxy substituiertes Benzyl, für gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C₁-C₄-­Alkyl und/oder C₁-C₄-Alkoxy substituiertes Phenyl, für Naphthyl, für jeweils gegebenen­falls durch Fluor, Chlor, Brom, Cyano, Nitro und/oder C₁-C₄-Alkyl substituiertes Pyridyl, Furyl oder Thienyl, für C₁-C₆-Alkoxy, Phenoxy, C₁-C₆-Alkylthio, Phenylthio, C₁-C₆-Alkyl­amino, Di-(C₁-C₄)-alkylamino, C₃-C₆-Cyclo­alkylamino oder für gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C₁-C₄-Alkyl, Trifluormethyl, C₁-C₄-Alkoxy und/oder C₁-C₄-­Alkoxy-carbonyl substituiertes Phenylamino steht und
R¹⁰ für gegebenenfalls durch Fluor und/oder Chlor substituiertes C₁-C₆-Alkyl, für gegebenenfalls durch Fluor, Chlor, Brom, Cyano, Nitro, C₁-C₄-­Alkyl, Trifluormethyl, C₁-C₄-Alkoxy, Difluor­methoxy, Trifluormethoxy, C₁-C₄-Alkylthio, C₁-­C₄-Alkylsulfinyl, C₁-C₄-Alkylsulfonyl, Di-(C₁-­C₂)alkylaminosulfonyl und/oder C₁-C₄-Alkoxy­carbonyl substituiertes Phenyl, für gegebenen­falls durch Chlor und/oder C₁-C₄-Alkyl substi­tuiertes Naphtyl oder für jeweils gegebenen­falls durch Fluor, Chlor, Brom, Cyano, Nitro und/oder C₁-C₄-Alkyl substituiertes Pyridyl oder Thienyl steht,
R¹¹ für Wasserstoff, Chlor oder Brom steht und
R¹² für C₁-C₆-Alkyl steht.2. Substituted phenoxybenzonitrile derivatives of the formula (I) according to Claim 1, in which
R¹ represents hydrogen, fluorine, chlorine, bromine, cyano or trifluoromethyl,
R² represents hydrogen, fluorine or chlorine,
R³ represents fluorine, chlorine, bromine, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl,
R⁴ represents hydrogen, fluorine or chlorine,
R⁵ represents hydrogen, fluorine or chlorine and
R⁶ for the groupings
Figure imgb0043
 or
Figure imgb0044
 stands in what
R⁷ and R⁸ are the same or different and each independently represent hydrogen, C₁-C₆-alkoxy-carbonyl-ethyl, the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, where
R⁹ for C₁-C₆-alkyl optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkoxy and / or C₁-C₄-alkoxy-carbonyl, for C₂-C₄-alkenyl optionally substituted by fluorine, chlorine and / or bromine, for C₂-C₄-alkynyl, optionally by fluorine, chlorine, bromine, C₁-C₄-alkyl and / or C₁-C₄-alkoxy-carbonyl substituted C₃-C₆-cycloalkyl, optionally substituted by fluorine, chlorine, bromine and / or C₁-C₄-alkyl substituted C₃-C₆-cycloalkyl-C₁-C₂-alkyl, optionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl and / or C₁-C₄-alkoxy substituted benzyl, for phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl and / or C₁-C₄-alkoxy, for naphthyl, each optionally substituted by fluorine, chlorine , Bromine, cyano, nitro and / or C₁-C₄-alkyl substituted pyridyl, furyl or thienyl, for C₁-C₆-alkoxy, phenoxy, C₁-C₆-alkylthio, phenylthio, C₁-C₆-alkylamino, di- (C₁-C₄ ) -alkylamino, C₃-C₆-cycloalkylamino or phenylamino optionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy and / or C₁-C₄-alkoxy-carbonyl and
R¹⁰ for optionally substituted by fluorine and / or chlorine C₁-C₆-alkyl, for optionally by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, trifluoromethyl, C₁-C₄-alkoxy, difluoromethoxy, trifluoromethoxy, C₁-C₄ -Alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, di- (C₁-C₂) alkylaminosulfonyl and / or C₁-C₄-alkoxycarbonyl substituted phenyl, optionally substituted by chlorine and / or C₁-C₄-alkyl or for naphthyl each is optionally substituted by fluorine, chlorine, bromine, cyano, nitro and / or C₁-C₄-alkyl pyridyl or thienyl,
R¹¹ represents hydrogen, chlorine or bromine and
R¹² is C₁-C₆ alkyl. 3. Substituierte Phenoxybenzonitril-Derivate der Formel (I) gemäß Anspruch 1, in welcher
R¹ für Wasserstoff, Fluor oder Chlor steht,
R² für Wasserstoff, Fluor oder Chlor steht,
R³ für Trifluormethyl steht,
R⁴ für Wasserstoff, Fluor oder Chlor steht,
R⁵ für Wasserstoff, Fluor oder Chlor steht,
R⁶ für die Gruppierungen
Figure imgb0045
 oder
Figure imgb0046
 steht, worin
R⁷ für Wasserstoff oder Acetyl steht und
R⁸ für Wasserstoff, Methoxycarbonylethyl, Eth­oxycarbonylethyl, die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ steht, wobei
R⁹ für gegebenenfalls durch Chlor, Brom, Methoxy oder Ethoxy substituiertes C₁-C₄-Alkyl, für Cyclopropyl, für Benzyl, für gegebenenfalls durch Fluor, Chlor, Brom, Methyl, Ethyl, Methoxy und/oder Ethoxy substituiertes Phenyl, für C₁-C₄-Alkoxy, Phenoxy, C₁-C₄-Alkylamino, Dimethylamino, Diethylamino, Cyclopentyl­amino, Cyclohexylamino oder für gegegebenen­falls durch Fluor, Chlor, Methyl, Ethyl, Tri­fluormethyl, Methoxy und/oder Ethoxy substitu­iertes Phenylamino steht und
R¹⁰ für gegebenenfalls durch Fluor und/oder Chlor substituiertes C₁-C₄-Alkyl, für gegebenen­falls durch Fluor, Chlor, Brom, Methyl, Tri­fluormethoxy, Dimethylaminosulfonyl und/oder Methoxycarbonyl substituiertes Phenyl steht,
R¹¹ für Wasserstoff, Chlor oder Brom steht und
R¹² für C₁-C₄-Alkyl steht.3. Substituted phenoxybenzonitrile derivatives of the formula (I) according to Claim 1, in which
R¹ represents hydrogen, fluorine or chlorine,
R² represents hydrogen, fluorine or chlorine,
R³ represents trifluoromethyl,
R⁴ represents hydrogen, fluorine or chlorine,
R⁵ represents hydrogen, fluorine or chlorine,
R⁶ for the groupings
Figure imgb0045
 or
Figure imgb0046
 stands in what
R⁷ represents hydrogen or acetyl and
R⁸ represents hydrogen, methoxycarbonylethyl, ethoxycarbonylethyl, the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, wherein
R⁹ for C₁-C₄-alkyl optionally substituted by chlorine, bromine, methoxy or ethoxy, for cyclopropyl, for benzyl, for phenyl optionally substituted by fluorine, chlorine, bromine, methyl, ethyl, methoxy and / or ethoxy, for C₁-C₄- Alkoxy, phenoxy, C₁-C₄-alkylamino, dimethylamino, diethylamino, cyclopentylamino, cyclohexylamino or phenylamino optionally substituted by fluorine, chlorine, methyl, ethyl, trifluoromethyl, methoxy and / or ethoxy and
R¹⁰ represents C₁-C₄-alkyl optionally substituted by fluorine and / or chlorine, represents phenyl optionally substituted by fluorine, chlorine, bromine, methyl, trifluoromethoxy, dimethylaminosulfonyl and / or methoxycarbonyl,
R¹¹ represents hydrogen, chlorine or bromine and
R¹² is C₁-C₄ alkyl. 4. Verfahren zur Herstellung von substituierten Phenoxybenzonitril-Derivaten der Formel (I),
Figure imgb0047
 in welcher
R¹ für Wasserstoff, Halogen, Cyano oder Trifluormethyl steht,
R² für Wasserstoff oder Halogen steht,
R³ für Halogen, Trifluormethyl, Trifluor­methoxy oder Trifluormethylsulfonyl steht,
R⁴ für Wasserstoff oder Halogen steht,
R⁵ für Wasserstoff oder Halogen steht und
R⁶ für die Gruppierungen
Figure imgb0048
 oder
Figure imgb0049
 steht, worin
R⁷ und R⁸ gleich oder verschieden sind und unabhängig voneinander jeweils für Wasserstoff, Alkoxycarbonylethyl, die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ stehen, wobei
R⁹ für jeweils gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cyclo­alkylalkyl, Benzyl, Phenyl, Naphthyl, Pyridyl, Furyl, Thienyl, Alkoxy, Phenoxy, Alkylthio, Phenylthio, Alkylamino, Dialkylamino, Cyclo­alkylamino oder Phenylamino steht und
R¹⁰ für jeweils gegebenenfalls substituiertes Alkyl, Phenyl, Naphthyl, Pyridyl oder Thienyl steht,
R¹¹ für Wasserstoff oder Halogen steht und
R¹² für Alkyl steht,
dadurch gekennzeichnet, daß man (a) für den Fall, daß in Formel (I) R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
Halogen-benzol-Derivate der allgemeinen Formel (II)
Figure imgb0050
 in welcher
R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben und
X für Halogen steht,
mit 2-Amino-4-hydroxy-benzonitril der Formel (III)
Figure imgb0051
 gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungs­mittels umsetzt, oder daß man (b) für den Fall, daß in Formel (I) R⁶ für die Gruppierung
Figure imgb0052
 steht, worin R⁷ und/oder R⁸ für die Gruppierung -CO-R⁹ oder die Gruppierung -SO₂-R¹⁰ stehen, und R¹, R², R³, R⁴, R⁵, R⁹ und R¹⁰ die oben angegebene Bedeutung haben,
Verbindungen der allgemeinen Formel (I), in welcher R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
mit Verbindungen der allgemeinen Formel (IV)
X¹-CO-R⁹      (IV)
in welcher
R⁹ die oben angegebene Bedeutung hat und
X¹ für Halogen steht,
oder mit Verbindungen der allgemeinen Formel (V)
X²-SO₂-R¹⁰      (V)
in welcher
R¹⁰ die oben angegebene Bedeutung hat und
X² für Halogen steht,
gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungs­mittels umsetzt, oder daß man (c) für den Fall, daß in Formel (I) R⁶ für die Guppierung
Figure imgb0053
 steht, worin R⁷ und/oder R⁸ für Alkoxycarbonylethyl stehen, und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
Verbindungen der allgemeinen Formel (I), in welcher R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die
oben angegebenen Bedeutungen haben,
mit Acrylsäureestern der Formel (VI)
CH₂=CH-COOR¹²      (VI)
in welcher
R¹² für Alkyl steht,
gegebenenfalls in Gegenwart eines basischen Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder daß man d) für den Fall, daß in Formel (I) R⁶ für die Gruppierung
Figure imgb0054
 steht, worin R¹¹ für Halogen steht und R¹² für Alkyl steht sowie R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben.
Verbindungen der allgemeinen Formel (I), in welcher R⁶ für Amino steht und R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeutungen haben,
mit Natriumnitrit oder Kaliumnitrit und mit einem Hydrogenhalogenid (HX³) in Gegenwart von Wasser und gegebenenfalls in Gegenwart eines organischen Lösungsmittels umsetzt und die hierbei gebildeten Diazoniumsalze der allge­meinen Formel (VII)
Figure imgb0055
 in welcher
R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeu­tungen haben und
X³ für Halogen steht,
mit Acrylsäureestern der Formel (VI)
CH₂=CH-COOR¹²      (VI)
in welcher
R¹² für Alkyl steht,
in Gegenwart von Hydrogenhalogeniden (HX³), gegebenenfalls in Gegenwart von Katalysatoren und gegebenenfalls in Gegenwart von Wasser und dem gegebenenfalls bei der Erzeugung der Verbindungen der Formel (VII) verwendeten organischen Lösungsmittel umsetzt, oder daß man (e) für den Fall, daß in Formel (I) R⁶ für die Gruppierung
Figure imgb0056
 steht, worin R¹¹ für Wasser­stoff steht und R¹² für Alkyl steht sowie R¹, R²,
R³, R⁴, und R⁵ die oben angegebenen Bedeutungen haben,
Verbindungen der allgemeinen Formel (I), in welcher
R⁶ für die Gruppierung
Figure imgb0057
 steht, worin R¹¹ für Halogen steht und R¹² für Alkyl steht sowie R¹, R², R³, R⁴ und R⁵ die oben angegebenen Bedeu­tungen haben,
mit einem Dehalogenierungsmittel, gegebenenfalls in Gegenwart eines Katalysators und gegebenenfalls in Gegenwart eines Verdünnungsmittels, umsetzt. 4. Process for the preparation of substituted phenoxybenzonitrile derivatives of the formula (I),
Figure imgb0047
 in which
R¹ represents hydrogen, halogen, cyano or trifluoromethyl,
R² represents hydrogen or halogen,
R³ represents halogen, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl,
R⁴ represents hydrogen or halogen,
R⁵ represents hydrogen or halogen and
R⁶ for the groupings
Figure imgb0048
 or
Figure imgb0049
 stands in what
R⁷ and R⁸ are the same or different and each independently represent hydrogen, alkoxycarbonylethyl, the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, where
R⁹ represents optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, benzyl, phenyl, naphthyl, pyridyl, Furyl, thienyl, alkoxy, phenoxy, alkylthio, phenylthio, alkylamino, dialkylamino, cycloalkylamino or phenylamino and
R¹⁰ represents optionally substituted alkyl, phenyl, naphthyl, pyridyl or thienyl,
R¹¹ represents hydrogen or halogen and
R¹² represents alkyl,
characterized in that one (a) in the case that in formula (I) R⁶ is amino and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
Halogen benzene derivatives of the general formula (II)
Figure imgb0050
 in which
R¹, R², R³, R⁴ and R⁵ have the meanings given above and
X represents halogen,
with 2-amino-4-hydroxy-benzonitrile of the formula (III)
Figure imgb0051
 if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or that (b) in the event that in formula (I) R⁶ for the grouping
Figure imgb0052
 in which R⁷ and / or R⁸ represent the grouping -CO-R⁹ or the grouping -SO₂-R¹⁰, and R¹, R², R³, R⁴, R⁵, R⁹ and R¹⁰ have the meaning given above,
Compounds of the general formula (I) in which R⁶ represents amino and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
with compounds of the general formula (IV)
X¹-CO-R⁹ (IV)
in which
R⁹ has the meaning given above and
X¹ represents halogen,
or with compounds of the general formula (V)
X²-SO₂-R¹⁰ (V)
in which
R¹⁰ has the meaning given above and
X² represents halogen,
if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, or that (c) in the event that in formula (I) R⁶ for the grouping
Figure imgb0053
 in which R⁷ and / or R⁸ are alkoxycarbonylethyl, and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
Compounds of the general formula (I) in which R⁶ is amino and R¹, R², R³, R⁴ and R⁵ are
have the meanings given above,
with acrylic acid esters of the formula (VI)
CH₂ = CH-COOR¹² (VI)
in which
R¹² represents alkyl,
if appropriate in the presence of a basic catalyst and if appropriate in the presence of a diluent, or that d) in the event that in formula (I) R⁶ for the grouping
Figure imgb0054
 is where R¹¹ is halogen and R¹² is alkyl and R¹, R², R³, R⁴ and R⁵ have the meanings given above.
Compounds of the general formula (I) in which R⁶ represents amino and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
with sodium nitrite or potassium nitrite and with a hydrogen halide (HX³) in the presence of water and optionally in the presence of an organic solvent and the diazonium salts of the general formula (VII) formed in this way
Figure imgb0055
 in which
R¹, R², R³, R⁴ and R⁵ have the meanings given above and
X³ represents halogen,
with acrylic acid esters of the formula (VI)
CH₂ = CH-COOR¹² (VI)
in which
R¹² represents alkyl,
in the presence of hydrogen halides (HX³), if appropriate in the presence of catalysts and if appropriate in the presence of water and the organic solvent optionally used in the preparation of the compounds of the formula (VII), or in that (e) in the event that in formula (I) R⁶ for the grouping
Figure imgb0056
 in which R¹¹ is hydrogen and R¹² is alkyl and R¹, R²,
R³, R⁴, and R⁵ have the meanings given above,
Compounds of the general formula (I) in which
R⁶ for grouping
Figure imgb0057
 in which R¹¹ is halogen and R¹² is alkyl and R¹, R², R³, R⁴ and R⁵ have the meanings given above,
with a dehalogenating agent, optionally in the presence of a catalyst and optionally in the presence of a diluent. 5. Herbizide und pflanzenwuchsregulierende Mittel, gekennzeichnet durch einen Gehalt an mindestens einem substituierten Phenoxybenzonitril-Derivat der Formel (I) gemäß den Ansprüchen 1 bis 4.5. Herbicides and plant growth regulators, characterized in that they contain at least one substituted phenoxybenzonitrile derivative of the formula (I) according to Claims 1 to 4. 6. Verfahren zur Bekämpfung von Unkräutern und zur Regulierung des Pflanzenwachstums, dadurch ge­kennzeichnet, daß man substituierte Phenoxybenzo­nitril-Derivate der Formel (I) gemäß den Ansprüchen 1 bis 4 auf die Unkräuter bzw. Pflanzen und/oder ihren Lebensraum einwirken läßt.6. A method for controlling weeds and for regulating plant growth, characterized in that substituted phenoxybenzonitrile derivatives of the formula (I) according to Claims 1 to 4 are allowed to act on the weeds or plants and / or their habitat. 7. Verwendung von substituierten Phenoxybenzonitril-­Derivaten der Formel (I) gemäß den Ansprüchen 1 bis 4 zur Bekämpfung von Unkräutern und/oder als Pflanzenwachstumsregulatoren.7. Use of substituted phenoxybenzonitrile derivatives of the formula (I) according to Claims 1 to 4 for combating weeds and / or as plant growth regulators. 8. Verfahren zur Herstellung von herbiziden und/oder pflanzenwuchsregulierenden Mitteln, dadurch gekenn­zeichnet, daß man substituierte Phenoxybenzonitril-­Derivate der Formel (I) gemäß den Ansprüchen 1 bis 4 mit Streckmitteln und/oder oberflächenaktiven Substanzen vermischt.8. A process for the preparation of herbicidal and / or plant growth-regulating agents, characterized in that substituted phenoxybenzonitrile derivatives of the formula (I) according to Claims 1 to 4 are mixed with extenders and / or surface-active substances.
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR910100162A (en) * 1990-04-27 1992-07-30 Fujisawa Pharmaceutical Co Method of producing alkanesulfonanilide derivatives
US5519133A (en) * 1995-06-02 1996-05-21 American Cyanamid Co. 3-(3-aryloxyphenyl)-1-(substituted methyl)-s-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5604180A (en) * 1995-06-02 1997-02-18 Crews, Jr.; Alvin D. 3-(3-aryloxyphenyl)-1 (substituted methyl)-s-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5654256A (en) * 1995-06-02 1997-08-05 American Cyanamid Company 3-(3-aryloxyphenyl)-1-(substituted methyl)-s-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5670641A (en) * 1995-06-02 1997-09-23 American Cyanamid Company 3-(3-aryloxyphenyl)-1-(substituted methyl)-S-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5763605A (en) * 1995-06-02 1998-06-09 American Cyanamid Company 3-(3-aryloxyphenyl)-1-(substituted methyl)-S-triazine-2,4,6-oxo or thiotrione herbicidal agents
US7235576B1 (en) * 2001-01-12 2007-06-26 Bayer Pharmaceuticals Corporation Omega-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US7678811B2 (en) 2002-02-11 2010-03-16 Bayer Healthcare Llc Pyridine, quinoline, and isoquinoline N-oxides as kinase inhibitors
US7838541B2 (en) 2002-02-11 2010-11-23 Bayer Healthcare, Llc Aryl ureas with angiogenesis inhibiting activity
US7897623B2 (en) 1999-01-13 2011-03-01 Bayer Healthcare Llc ω-carboxyl aryl substituted diphenyl ureas as p38 kinase inhibitors
US8076488B2 (en) 2003-02-28 2011-12-13 Bayer Healthcare Llc Bicyclic urea derivatives useful in the treatment of cancer and other disorders
US8110587B2 (en) 2002-02-11 2012-02-07 Bayer Healthcare Llc Aryl ureas as kinase inhibitors
US8124630B2 (en) 1999-01-13 2012-02-28 Bayer Healthcare Llc ω-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
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US8637553B2 (en) 2003-07-23 2014-01-28 Bayer Healthcare Llc Fluoro substituted omega-carboxyaryl diphenyl urea for the treatment and prevention of diseases and conditions
US8796250B2 (en) 2003-05-20 2014-08-05 Bayer Healthcare Llc Diaryl ureas for diseases mediated by PDGFR

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039289A1 (en) * 1997-03-03 1998-09-11 Nissan Chemical Industries, Ltd. Urea derivatives, and industrial antibacterial and antifungal agents, algaecides and antiperiphytic agents containing the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0034402A2 (en) * 1980-02-05 1981-08-26 Imperial Chemical Industries Plc Method of preparing fluorine-substituted diphenyl ether derivatives and fluorine-substituted halogeno benzene derivatives for use therein
US4526608A (en) * 1982-07-14 1985-07-02 Zoecon Corporation Certain 2-pyridyloxyphenyl-oximino-ether-carboxylates, herbicidal compositions containing same and their herbicidal method of use
EP0166186A2 (en) * 1984-05-28 1986-01-02 Bayer Ag Derivatives of substituted phenoxyphenyl-propionic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0034402A2 (en) * 1980-02-05 1981-08-26 Imperial Chemical Industries Plc Method of preparing fluorine-substituted diphenyl ether derivatives and fluorine-substituted halogeno benzene derivatives for use therein
US4526608A (en) * 1982-07-14 1985-07-02 Zoecon Corporation Certain 2-pyridyloxyphenyl-oximino-ether-carboxylates, herbicidal compositions containing same and their herbicidal method of use
EP0166186A2 (en) * 1984-05-28 1986-01-02 Bayer Ag Derivatives of substituted phenoxyphenyl-propionic acid

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR910100162A (en) * 1990-04-27 1992-07-30 Fujisawa Pharmaceutical Co Method of producing alkanesulfonanilide derivatives
US5519133A (en) * 1995-06-02 1996-05-21 American Cyanamid Co. 3-(3-aryloxyphenyl)-1-(substituted methyl)-s-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5604180A (en) * 1995-06-02 1997-02-18 Crews, Jr.; Alvin D. 3-(3-aryloxyphenyl)-1 (substituted methyl)-s-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5654256A (en) * 1995-06-02 1997-08-05 American Cyanamid Company 3-(3-aryloxyphenyl)-1-(substituted methyl)-s-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5670641A (en) * 1995-06-02 1997-09-23 American Cyanamid Company 3-(3-aryloxyphenyl)-1-(substituted methyl)-S-triazine-2,4,6-oxo or thiotrione herbicidal agents
US5763605A (en) * 1995-06-02 1998-06-09 American Cyanamid Company 3-(3-aryloxyphenyl)-1-(substituted methyl)-S-triazine-2,4,6-oxo or thiotrione herbicidal agents
US8841330B2 (en) 1999-01-13 2014-09-23 Bayer Healthcare Llc Omega-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US8124630B2 (en) 1999-01-13 2012-02-28 Bayer Healthcare Llc ω-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US7897623B2 (en) 1999-01-13 2011-03-01 Bayer Healthcare Llc ω-carboxyl aryl substituted diphenyl ureas as p38 kinase inhibitors
US7235576B1 (en) * 2001-01-12 2007-06-26 Bayer Pharmaceuticals Corporation Omega-carboxyaryl substituted diphenyl ureas as raf kinase inhibitors
US8071616B2 (en) 2002-02-11 2011-12-06 Bayer Healthcare Llc Pyridine, quinoline, and isoquinoline N-oxides as kinase inhibitors
US8110587B2 (en) 2002-02-11 2012-02-07 Bayer Healthcare Llc Aryl ureas as kinase inhibitors
US7838541B2 (en) 2002-02-11 2010-11-23 Bayer Healthcare, Llc Aryl ureas with angiogenesis inhibiting activity
US8242147B2 (en) 2002-02-11 2012-08-14 Bayer Healthcare Llc Aryl ureas with angiogenisis inhibiting activity
US8618141B2 (en) 2002-02-11 2013-12-31 Bayer Healthcare Llc Aryl ureas with angiogenesis inhibiting activity
US7678811B2 (en) 2002-02-11 2010-03-16 Bayer Healthcare Llc Pyridine, quinoline, and isoquinoline N-oxides as kinase inhibitors
US9181188B2 (en) 2002-02-11 2015-11-10 Bayer Healthcare Llc Aryl ureas as kinase inhibitors
US8076488B2 (en) 2003-02-28 2011-12-13 Bayer Healthcare Llc Bicyclic urea derivatives useful in the treatment of cancer and other disorders
US8796250B2 (en) 2003-05-20 2014-08-05 Bayer Healthcare Llc Diaryl ureas for diseases mediated by PDGFR
US8637553B2 (en) 2003-07-23 2014-01-28 Bayer Healthcare Llc Fluoro substituted omega-carboxyaryl diphenyl urea for the treatment and prevention of diseases and conditions
US8207166B2 (en) 2004-04-30 2012-06-26 Bayer Healthcare Llc Substituted pyrazolyl urea derivatives useful in the treatment of cancer

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